School of Mechanical and Industrial Engineering

Materials Science and Engineering

Engineering Materials II
Course Instructor: Gezaei Abera Compiled: April, 2020

Corrosion and Degradation of Materials

 Corrosion and Degradation of Materials

Content Outline

 Introduction to corrosion and degradation  Forms of corrosion

 Corrosion of metals  corrosion prevention
 Electrode potentials  Corrosion of ceramics
 Corrosion rate  Degradation of polymers
 Prediction of corrosion rates
 Activation polarization
 Environmental effect
 Introduction to Corrosion and Degradation

 Most materials experience some type of interaction with the environments.

 Deteriorative mechanisms are different for the three material types.
 In metals, there is actual material loss either by corrosion or 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.
 In polymers, mechanisms and consequences differ from those for metals and
ceramics, and the term degradation is most frequently used.
 Polymers may dissolve when exposed to a liquid solvent. They may absorb the
solvent and swell; also, electromagnetic radiation and heat.
 Corrosion of Metals

 Corrosion is defined as the destructive and unintentional attack on a metal.

 It is electrochemical and ordinarily begins at the surface of the metal.

 About 5% of an industrialized nation’s income is spent due to corrosion.

 All metals are not equally susceptible to corrosion.

 The consequences of corrosion are all too common. Examples, the rusting of automotive

body panels and radiator and exhaust components.

 Corrosion processes are occasionally used to advantage. For example, etching procedures,
use the selective chemical reactivity of grain boundaries or various microstructural
constituents.
 Electrochemical Considerations

 For metallic materials, the corrosion process is normally electrochemical, that is

chemical reaction in which there is transfer of electrons from one chemical species
to another.
 Metal atoms characteristically lose or give up electrons in what is called an
oxidation reaction.
 Hypothetical metal M that has a valence of n may experience oxidation according
to the reaction.
 The site at which oxidation takes place is called the anode.
 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.
 Example, some metals undergo corrosion in acid solutions, which have a high
concentration of hydrogen (H) ions; the H ions are reduced as follows:

 Metal may be totally reduced from an ionic to a neutral metallic state according
to:

 That location at which reduction occurs is called the cathode.

 Electrochemical Considerations

 zinc will experience oxidation or corrosion.  The electrochemical reactions

associated with the corrosion of
zinc in an acid solution.
 Electrochemical Considerations

 Since zinc is a metal, and therefore a good electrical conductor, these electrons may
be transferred to an adjacent region at which the H ions are reduced according to

Total reaction:
 Electrode Potentials

 Not all metallic materials oxidize to form ions with the same degree of ease.
 An electrochemical cell consisting of iron and copper electrodes.
 If the iron and copper electrodes are connected electrically, reduction will occur for
copper at the expense of the oxidation of iron, as follows:

 Copper ion (Cu²⁺) will deposit as metallic copper on

the copper electrode, while iron dissolves (corrodes)
on the other side of the cell and goes into solution.
 Electrode Potentials

 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.
 In addition, there will be some net ion motion from each cell to the other across the
membrane.
 This is called a galvanic couple — two metals electrically connected in a liquid
electrolyte wherein one metal becomes an anode and corrodes, while the other acts
as a cathode.
An electrochemical cell consisting of iron and zinc electrodes.
 Galvanic couple consisting of the same iron half-cell connected to a metal zinc
electrode that is immersed in a 1M solution.
 Electrode Potentials

 Zinc is the anode and corrodes, whereas the Fe now becomes the cathode.
 The standard EMF series

 These measured cell voltages represent only differences in electrical potential thus it
is convenient to establish a reference point, or reference cell, to which other cell
halves may be compared.

 This reference cell, arbitrarily chosen, is the

standard hydrogen electrode.
 It consists of an inert platinum electrode in a
1M H⁺ solutions.

The standard hydrogen reference half-cell

 The standard EMF series
The Standard EMF Series Table:
 EMF refers to the term
electromotive force.
 The EMF series is
generated by coupling to
the standard hydrogen
electrode.
 Standard half-cells for
various metals and ranking
them according to
measured voltage.
 The standard EMF series

 Consider the generalized reactions involving the oxidation of metal M 1 and the
reduction of metal M2 as:
 Concentration and Temperature on Cell Potential

 The cell potential is highly dependent on concentration and temperature.

 If M1 and M2 electrodes are pure metals, the cell potential depends on the absolute
temperature T and the molar ion concentrations according to the
Nernst equation:

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.

 At 25˚C (about room temperature) Nernst equation will be simplified as:

 Corrosion Penetration Rate (CPR)

 It is the rate of material removal as a consequence of the chemical action given by:

 If there is an electric current associated with electrochemical corrosion reactions

CPR will become:
Corrosion penetration rate (CPR)
 Prediction of Corrosion Rates

 Consider the standard Zn/H2 electrochemical cell.

 The potentials of the two electrodes will not be at the values determined from EMF
series because the system is now a non-equilibrium one.
 The displacement of each electrode potential from its equilibrium value is termed
polarization, and the magnitude of this displacement is the overvoltage (η ).

• Suppose that the zinc electrode in Figure above has a

potential of 0.621 V after it has been connected to
the platinum electrode.
• The equilibrium potential is 0.763 V (Table EMF),
and, therefore the overvoltage.
 Activation polarization

 It is the condition wherein the reaction rate is controlled by the one step in the series
that occurs at the slowest rate.

1. Adsorption of H ions from the solution onto the zinc

surface.
2. Electron transfer from the zinc to form a hydrogen atom,

3. Combining of two hydrogen atoms to form a molecule of

hydrogen,
4. The coalescence of many hydrogen molecules to form a
bubble.
Activation Polarization for Hydrogen Electrode

i0 = the exchange current density

 Activation Polarization for Hydrogen Electrode

Concentration polarization exists when the reaction rate is limited by

diffusion in the solution.

Figure 17.8 For hydrogen

reduction, schematic
representations of the H
distribution in the vicinity of
the cathode for;
(a) low reaction rates and/or
high concentrations and
(b) (b) high reaction rates
and/or low concentrations.
 Corrosion of Zinc in Acidic Solution

• Hydrogen and zinc experience

activation polarization along their
respective lines.
• Corrosion potential, designated Vc,
occurs when oxidation and reduction
rates are equal and the corresponding
corrosion current density ic.
• The corrosion rate of zinc (which also
corresponds to the rate of hydrogen
evolution) may thus be computed by
insertion of this ic value into:

Activation polarization of both cells

 Corrosion of Zinc in Acidic Solution
Passivity: under particular environmental conditions, some normally active metals and alloys, lose
their chemical reactivity and become extremely inert. This phenomenon is termed as passivity.
Passivity is displayed by chromium, iron, nickel, titanium, and many of their alloys.
 Environmental Effect

 The variables in the corrosion environment, which include fluid velocity, temperature, and
composition, can have a decided influence on the corrosion properties of the materials that are
in contact with it.
 Increasing fluid velocity enhances the rate of corrosion due to erosive effects.
 The rates of most chemical reactions rise with increasing temperature.
 Increasing the concentration of the corrosive species (e.g., H ions in acids) in many situations
produces a more rapid rate of corrosion.
 However, for materials capable of passivation, raising the corrosive content may result in an
active-to-passive transition, with a considerable reduction in corrosion.
 Cold working or plastically deforming ductile metals is used to increase their strength.
 A cold-worked metal is more susceptible to corrosion than the same material in an annealed
state.
Forms of Corrosion
 Uniform Attack

 Uniform attack is a form of electrochemical corrosion that occurs with

equivalent intensity over the entire exposed surface and often leaves
behind a scale or deposit.
 In a microscopic sense, the oxidation and reduction reactions occur
randomly over the surface.
 Some familiar examples include general rusting of steel and iron and the
tarnishing of silverware.
 Galvanic Corrosion

 It occurs when two metals or alloys having different compositions are electrically
coupled while exposed to an electrolyte.
 The less noble or more reactive metal in the particular environment will experience
corrosion the more inert metal, the cathode, will be protected from corrosion.
 For example, steel screws corrode when in contact with brass in a marine
environment if copper and steel tubing are joined in a domestic water heater, the
steel will corrode in the vicinity of the junction.
 The rate of galvanic attack depends on the relative anode-to-cathode surface areas
that are exposed to the electrolyte,
 The reason for high corrosion for small anode is that corrosion rate depends on
current density.
 Galvanic Corrosion

 The rate is related directly to the

cathode–anode area ratio; that is, for a

given cathode area, a smaller anode

will corrode more rapidly than a larger

one.

 Galvanic corrosion of a magnesium

shell that was cast around a steel core.

 Galvanic Corrosion

Measures to reduce Galvanic corrosion

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

together in the galvanic series.

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

area as large as possible.

c) Electrically insulate dissimilar metals from each other.

d) Electrically connect a third, anodic metal to the other two; this is a form of

cathodic protection.
 Crevice Corrosion

 It is caused by concentration differences of ions or dissolved gases in the electrolyte

solution, and between two regions of the same metal piece.

 A good example of this type of corrosion occurs under deposits of dirt or corrosion

products where the solution becomes stagnant and there is localized depletion of

dissolved oxygen.
 Crevice Corrosion

Mechanisms of Crevice corrosion:

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

this position according to:

 Electrons from this electrochemical

reaction are conducted through the

metal to adjacent external regions,

where they consumed by reduction.

 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.

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

in compositions.
 Pitting

 Specimens having polished surfaces display a greater resistance to pitting corrosion.

 Stainless steels are somewhat susceptible to this form of corrosion; however, alloying

with about 2% molybdenum enhances their resistance significantly.

 The pitting of a 304 stainless steel plate by an acid-chloride solution.

 Intergranular Corrosion

 Chromium carbide particles that have precipitated along grain boundaries in stainless

steel, and the attendant zones of chromium depletion.

 It occurs preferentially along grain boundaries.

 The net result is that a macroscopic specimen disintegrates along its grain boundaries.

 High temperature sensitized to intergranular attack.

 Heat treatment permits the formation of small precipitate

particles of chromium carbide (Cr23C6) by reaction

between the chromium and carbon in the stainless steel.

 Intergranular Corrosion

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

steels, when it is often termed weld decay.

 Intergranular corrosion in stainless steel can be minimized by:

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.
Intergranular Corrosion

Figure 17.19 Weld decay in a

stainless steel. The regions
along which the grooves
have formed were sensitized
as the weld cooled.
 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 material changes from yellow to a red or copper color.

 It can also occur with other alloy systems in which aluminum, iron, cobalt, chromium,

and other elements are vulnerable to preferential removal.

 Erosion-corrosion

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

abrasion or wear as a consequence of fluid motion.

 All metal alloys, to one degree or another, are susceptible to 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.
Ex. Propellers, turbine blades, valves, and pumps are also susceptible to this form of corrosion.
 Erosion-corrosion

 Impingement failure of an elbow

that was part of a steam condensate
line.
 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.
 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,
• brasses are especially vulnerable when exposed to ammonia.

Photomicrograph showing
intergranular stress corrosion
cracking in brass.
 Stress corrosion

Measure to take in reducing or eliminating stress

corrosion is :

• lower the magnitude of the stress by reducing

the external load or increasing the cross-

sectional area perpendicular to the applied

Figure 17.21: A bar of steel bent into a horseshoe
stress.
shape using a nut-and-bolt assembly. While
• appropriate heat treatment may be used to immersed in seawater, stress corrosion cracks
formed along the bend at those regions where the
anneal out any residual thermal stresses.
tensile stresses are the greatest.
 Hydrogen Embrittlement

 Hydrogen embrittlement is similar to stress corrosion. It is the penetration of atomic hydrogen (H)

into the material which reduces the strength and ductility of a material.

 The terms hydrogen induced cracking and hydrogen stress cracking are sometimes also used.

 In order for hydrogen embrittlement to occur, some source of hydrogen must be present,

 High-strength steels are susceptible to hydrogen embrittlement, and increasing strength tends to

enhance the material’s susceptibility. Techniques commonly used to reduce the likelihood of

hydrogen embrittlement include:

 reducing the tensile strength of the alloy via a heat treatment;
 removal of the source of hydrogen; ‘‘baking’’ the alloy at an elevated temperature.
 to drive out any dissolved hydrogen; and substitution of a more embrittlement resistant alloy.
 Corrosion Prevention
Corrosion prevention methods:
1. Cathodic protection
2. Oxidation
Cathodic protection: simply involves supplying, from an external source, electrons to the metal
to be protected, making it a cathode.
• Cathodic protection technique employs a galvanic couple: the metal to be protected is
electrically connected to another metal that is more reactive in the particular environment.
• The latter experiences oxidation, and, upon giving up electrons, protects the first metal from
corrosion.
• The oxidized metal is often called a sacrificial anode.
• Magnesium and zinc are commonly used as such because they lie at the anodic end of the
galvanic series.
 Corrosion Prevention
Cathodic protection:

An underground tank using an impressed current.

An underground
The negative terminal of the power source is connected to the structure to be
pipeline using a
protected.
magnesium
The other terminal is joined to an inert anode (often graphite), which is, in this
sacrificial anode . case, buried in the soil; high-conductivity backfill material provides good
electrical contact between the anode and surrounding soil.
 Corrosion Prevention
Cathodic protection:

 Process of galvanizing is simply one in

which a layer of zinc is applied to the
surface of steel by hot dipping.
 Corrosion of the zinc coating will proceed at
an extremely slow rate because the ratio of
the anode-to-cathode surface area is quite
large.
 Galvanic protection of steel as provided by a
coating of zinc.
 Corrosion Prevention

Oxidation:

 Gaseous atmosphere Produces oxide layer:

 M²⁺ ions must diffuse away from the metal–scale

interface, and/or O²- ions must diffuse toward this same
interface.
 The oxide scale serves both as an electrolyte and
electrical circuit for the passage of electrons.
 protect the metal from rapid oxidation when it acts as a
barrier to ionic diffusion and/or electrical conduction;
 Rate of Oxidation

 Rate of oxidation (i.e., the rate of film thickness increase) and the tendency of the

film to protect the metal from further oxidation are related to the relative volumes

of the oxide and metal.

• Pilling–Bedworth • Pilling–Bedworth
ratio for a divalent ratio for a metal that
metal – dependence is not divalent
on the densities and
atomic/formula
weights of the metal
and its oxide:
 Corrosion of Ceramics

Corrosion of ceramic materials:

 Ceramic materials, being inherently corrosion resistant,

are frequently used at elevated temperatures and/or in

extremely corrosive environments.

 Degradation of Polymers
 Polymeric materials also experience deterioration by means of environmental
interactions.
 However, an undesirable interaction is specified as degradation rather than corrosion
because the processes are basically dissimilar.
 Whereas most metallic corrosion reactions are electrochemical, polymeric
degradation is physiochemical; it involves physical as well as chemical phenomena.
 Polymers may deteriorate by swelling and dissolution.
 Covalent bond rupture as a result of heat energy, chemical reactions, and radiation is
also possible.
 Because of the chemical complexity of polymers, their degradation mechanisms are
not well understood.
 Degradation of Polymers
 When polymers are exposed to liquids, the main forms of degradation are swelling
and dissolution.
 With swelling, the liquid or solute diffuses into and is absorbed within the polymer.
 The small solute molecules fit into and occupy positions among the polymer
molecules.
 Swelling may be considered a partial dissolution process in which there is only
limited solubility of the polymer in the solvent.
 Swelling and dissolution traits also are affected by temperature, as well as by the
characteristics of the molecular structure.
 Increasing molecular weight, increasing degree of crosslinking and crystallinity, and
decreasing temperature result in a reduction of these deteriorative processes.
 Degradation of Polymers

 In general, polymers are

much more resistant to attack
by acidic and alkaline
solutions than are metals.
 For example, hydrofluoric
acid (HF) corrodes many
metals as well as etch and
dissolve glass, so it is stored
in plastic bottles.