MATERIAL SCIENCES

and ENGINEERING
Module 8: Corrosion and Degradation of
Materials

ME 260: INTRODUCTION TO ENGINEERING MATERIALS 1.1

 Table of Content
Module 9:
Corrosion and Degradation of Materials

Gospel Reading ……………………………….. 1

Course Learning Outcomes……………………. 2

ME 260: INTRODUCTION TO ENGINEERING MATERIALS 1.2

 Gospel Reading

Let us put ourselves in the presence of God..

In the name of the Father, the Son, and the Holy
Spirit..
Isaiah 40:11: He tends his flock like a shepherd:
He gathers the lambs in his arms and carries
them close to his heart.
St. John the Baptist de la Salle..Pray for us..Live
Jesus in our hearts.. Forever.

ME 260: INTRODUCTION TO ENGINEERING MATERIALS 1.3

 4

ME 260: INTRODUCTION TO ENGINEERING MATERIALS 1.4

 REFERENCES:
1.Clark, Donald S. 3rd ed. (1959). Engineering Materials
and Processes. UK: TBS The Book Service Ltd.
2.Callister Jr., William D. (2001). Fundamentals of Material
Science and Engineering. NY: John Wiley & sons
3.Askeland, Donald, R. 3rd ed (1993). The Science and
Engineering of Materials. USA: Brooks and Cole
4.Ashby, Michael F. 4th ed. (2007). Materials: Engineering,
Science, processing and Design. Butterworth-Heinemann.

ME 260: INTRODUCTION TO ENGINEERING MATERIALS 1.5

 CORROSION AND

DEGRADATION
OF MATERIALS
Corrosion and Degradation of Materials

WHY STUDY Corrosion and Degradation of Materials?

With a knowledge of the types of and an understanding of the
mechanisms and causes of corrosion and degradation, it is
possible to take measures to prevent them from occurring. For
example, we may change the nature of the environment, select
a material that is relatively nonreactive, and/or protect the
material from appreciable deterioration.
Corrosion and Degradation of Materials

Course Learning Objective:

•Definesand analyze corrosion and

degradation of engineering materials.
Corrosion and Degradation of Materials
Introduction

Deteriorative mechanisms are different for the three material

types. In metals, there is actual material loss either by dissolution
(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 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, or they may absorb the solvent
and swell; also, electromagnetic radiation (primarily ultraviolet)
and heat may cause alterations in their molecular structures.
Corrosion and Degradation of Materials

Corrosion of Metals
Corrosion is defined as the destructive and unintentional attack of a metal; it is
electrochemical and ordinarily begins at the surface. The problem of metallic
corrosion is one of significant proportions; in economic terms, it has been
estimated that approximately 5% of an industrialized nation’s income is spent
on corrosion prevention and the maintenance or replacement of products lost
or contaminated as a result of corrosion reactions.

Electrochemical Considerations
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. Metal atoms characteristically lose or give up
electrons in what is called an oxidation reaction.
Corrosion and Degradation of Materials
Corrosion of Metals
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

Figure 11 An electrochemical cell consisting

of iron and copper electrodes, each of which
is immersed in a 1 M solution of its ion. Iron
corrodes while copper electrodeposits.
 Corrosion and Degradation of Materials
Corrosion of Metals
The Standard emf Series

These measured cell voltages represent

only differences in electrical potential, and Figure 12-The
thus it is convenient to establish a Standard
hydrogen
reference point, or reference cell, to reference
which other cell halves may be half-cell.
compared. This reference cell, arbitrarily
chosen, is the standard hydrogen
electrode (Figure 17.4). It consists of an
inert platinum electrode in a 1 M solution
of H ions, saturated with hydrogen gas
that is bubbled through the solution at a
pressure of 1 atm and a temperature of
 Corrosion and Degradation of Materials
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. The formula for this calculation is

where W is the weight loss after exposure time t; and A

represent the density and exposed specimen area,
respectively, and K is a constant, its magnitude depending on
the system of units used
where, again, n is the number of electrons associated with the
ionization of each metal atom, and f is 96,500 C/mol.
 Corrosion and Degradation of Materials
Concentration Polarization
Concentration polarization exists when the reaction rate is limited by diffusion in
the solution. For example, consider again the hydrogen evolution reduction
reaction

Figure 13- For reduction

reactions, schematic plots of
overvoltage versus logarithm of
current density for (a)
concentration polarization, and
(b) combined activation-
concentration polarization.
 Corrosion and Degradation of Materials
PASSIVITY
Some normally active metals and alloys, under particular environmental
conditions, lose their chemical reactivity and become extremely inert. This
phenomenon, termed passivity, is displayed by chromium, iron, nickel, titanium,
and many of their alloys. It is felt that 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. Stainless steels are
highly resistant to corrosion in a rather wide variety of atmospheres as a result of
passivation.

ENVIRONMENTAL EFFECTS
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. In most instances,
 Corrosion and Degradation of Materials
ENVIRONMENTAL EFFECTS

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. The rates of most chemical reactions rise with
increasing temperature; this also holds for most corrosion
situations. Increasing the concentration of the corrosive species
(e.g., H* ions in acids) in many situations produces a more rapid
rate of corrosion. Cold working or plastically deforming ductile
metals is used to increase their strength; however, a cold-worked
metal is more susceptible to corrosion than the same material in
an annealed state.
 Corrosion and Degradation of Materials
FORMS OF CORROSION
Metallic corrosion is sometimes classified into eight forms: uniform, galvanic,
crevice, pitting, intergranular, selective leaching, erosion–corrosion, and stress
corrosion.

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.

Galvanic corrosion occurs when two metals or alloys having different

compositions are electrically coupled while exposed to an electrolyte. 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; that is, for a given cathode area, a smaller anode will corrode more
rapidly than a larger one.
 Corrosion and Degradation of Materials
FORMS OF CORROSION
Electrochemical (Crevice) 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.
Corrosion preferentially occurring at these
Figure 14 On this plate, which was
positions is called crevice corrosion (Figure
immersed in seawater, crevice
14).
corrosion has occurred at the regions
that were covered by washers.
 Corrosion and Degradation of Materials
FORMS OF CORROSION

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. It is an extremely
insidious type of corrosion, often going undetected and with very little
material loss until failure occurs.
Intergranular corrosion occurs preferentially along grain boundaries for
some alloys and in specific environments. The net result is that a
macroscopic specimen disintegrates along its grain boundaries. This
type of corrosion is especially prevalent in some stainless steels.
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
 Corrosion and Degradation of Materials
FORMS OF 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.
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. In fact, some materials that
are virtually inert in a particular

Hydrogen Embrittlement wherein various metal alloys, specifically some

steels, experience a significant reduction in ductility and tensile strength
when atomic hydrogen (H) penetrates into the material.
Corrosion and Degradation of Materials
Corrosion Protection
Several measures may be taken to prevent, or at least reduce, corrosion.
These include material selection, environmental alteration, the use of
inhibitors, design changes, application of coatings, and cathodic
protection.
• With cathodic protection, the metal to be protected is made a cathode by
supplying electrons from an external source.

Oxidation

Oxidation of metal alloys is also possible in gaseous atmospheres,

normally air, wherein an oxide layer or scale forms on the surface of the
metal. This phenomenon is frequently termed scaling, tarnishing, or dry
corrosion. In this section we will discuss possible mechanisms for this type
of corrosion, the types of oxide layers that can form, and the kinetics of
oxide formation.
 Corrosion and Degradation of Materials
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, by contrast, polymeric degradation is physiochemical;
that is, it involves physical as well as chemical phenomena.
Bond Rupture
Polymers may also experience degradation by a process termed
scission—the severance or rupture of molecular chain bonds. This
causes a separation of chain segments at the point of scission and a
reduction in the molecular weight.
- Radiation Effects: Certain types of radiation [electron beams, x-rays, -
and -rays, and ultraviolet (UV) radiation] possess sufficient energy to
penetrate a polymer specimen and interact with the constituent atoms or
their electrons.
 Corrosion and Degradation of Materials
Degradation of Polymers
Chemical Reaction Effects
Oxygen, ozone, and other substances can cause or accelerate chain
scission as a result of chemical reaction. This effect is especially
prevalent in vulcanized rubbers that have doubly bonded carbon atoms
along the backbone molecular chains and hat are exposed to ozone
(O3), an atmospheric pollutant.
Thermal Effects
Thermal degradation corresponds to the scission of molecular chains at
elevated temperatures; as a consequence, some polymers undergo
chemical reactions in which gaseous species are produced. These
reactions are evidenced by a weight loss of material; a polymer’s
thermal stability is a measure of its resilience to this decomposition.
Thermal stability is related primarily to the magnitude of the bonding
energies between the various atomic constituents of the polymer: higher
bonding energies result in more thermally stable materials.
 Corrosion and Degradation of Materials
Weathering
Many polymeric materials serve in applications that require
exposure to outdoor conditions. Any resultant degradation is
termed weathering, which may be a combination of several
different processes. Under these conditions deterioration is
prirmarily the result of oxidation, which is initiated by ultraviolet
radiation from the sun. Some polymers such as nylon and
cellulose are also susceptible to water absorption, which
produces a reduction in their hardness and stiffness. Resistance
to weathering among the various polymers is quite diverse.The
fluorocarbons are virtually inert under these conditions; but
some materials, including poly(vinyl chloride) and polystyrene,
are susceptible to weathering.
 Corrosion and Degradation of Materials
1. Seatwork
2. Problem Solving
3. Exercises

MATERIAL SELECTION PROCESSES 25

 26

ME 260: INTRODUCTION TO ENGINEERING MATERIALS 1.26