LECTURE 5 FRACTURE AND OXIDATION

5.1 FRACTURE

Fracture is a phenomenon you are quite familiar with in your daily experiences. Very often
you break a wooden stick or piece of chalk into two or many pieces, crush a stone/boulder
into small pieces to form ballast, etc. Each time you break a single object once you create
two new surfaces. We can thus define fracture as the separation of a surface into two
surfaces.

5.1.1 Types of Fracture

Generally, there two types of fracture: (i) ductile fracture, and (ii) brittle fracture.
The ductile fracture is generally characterized by the cup-and-cone shapes of the two new
surfaces created. Materials, (basically ductile materials such as steel, copper, or mostmetal)
which exhibit ductile fracture also show extensive necking prior to failure (fracture). Brittle
fracture, on the other hand is accompanied by very little, if any, necking. It occurs quite
suddenly without warning and in the case of tensile loading; the fracture path is nearly
perpendicular to the axis of the specimen. Examples of material whose fracture is brittle
include ceramics (e.g., chinaware, clay pots etc), glass products, and metals that have
been subjected to very cold temperatures (liquid nitrogen temperature ~ - 196 C or
77 K). Figure 5.1 shows schematically these two types offractures.

Fig. 5.1. Schematics depicting (a) ductile (b) brittle fractures.

Shown in figure 5.2 are photographs of components that have failed in either ductile or
brittle manner.
 Fig. 5.2 Tensile failures in steel specimens showing necking in mild-steel, (i) and (iii),
and brittle failure in high-strength steel, (ii).

5.1.2. Prevention of Brittle Fracture

Experience has shown that brittle materials always fail by brittle fracture. The origins of
the brittle fracture are mainly sharp microscopic/minute cracks (invisible to the nakedeye)
present either on the exterior surface or in the interior of the materials. These sharp cracks
act as stress concentrators (i.e., points around which the there is already very high stress)
such that when an external stress is applied to the material, the strength of the material is
easily exceeded even for small values of external stress, which otherwise would be
inadequate to cause failure. When the material strength is exceeded in the vicinity of the
crack, the crack begins to grow, leading to failure. Since the stress at the tip of the crack
is inversely proportional to the square root of the crack-tip radius, it isnow obvious that
one way of preventing brittle failure is to blunt the crack tips, particularly those of the
exterior microcracks. This can be achieved by etching using appropriate chemicals. Note
that etching is a process where a mildly corrosive liquid is applied to the surface of the
specimen and attack occurs along the grain boundaries or microcracks. The microcracks
are enlarged and blunted at the same time.

Fig. 5.3 A plate with a surface

 microcrack of length c and tip
radius 
 c


The other procedure of removing surface microcracks is by polishing using very fine
abrasives such as diamond lapping (extremely fine particles of diamond in liquid
suspension). Introduction of ductile fibres during the fabrication of certain brittle
components is another way of ensuring that failure through brittle fracture is minimized,
as the ductile fibres will prevent crack growth.
5.2. CORROSION

Before we proceed we shall define some terminologies that will recur frequently in this
section.

Anion An ion with a negative charge

Cation An ion with a positive charge
Ion An atom that has a net electric charge
Oxidation A reaction that generates electrons
Reduction A reaction that consumes electrons
Valency The characteristic number of electrons lost when a metal atom
becomes an ion
Free energy This the portion of the substance’s internal energy which is
available to do work

You are very familiar with rusting of iron or steel items. This is just an example of
corrosion. Corrosion can be defined as the degradation of metals by an electrochemical
reaction with the environment.

Metals are very important natural resources to human beings. It is therefore pertinent that
we understand corrosion and how to control it in order to sustain our technological
development and diminish the financial or material waste or inconvenience cost associated
with.

Activity:

List and explain a number of incidences you are aware of that

are associated with or attributed to corrosion to illustrate the
financial, material waste, and inconveniences to human society.

Question:
What, in your opinion causes corrosion to proceed?

You will learn in thermodynamics that there is a strong tendency for high-energy states to
transform into low energy states. It is this tendency that for metals, they combine with other
elements found in the environment, which leads to corrosion. For example, an iron oxide
is a low-energy state compared to pure iron. We now state that the driving force for
corrosion emanates from chemical energy. It is important, however, to point out that prior
to a reaction occurring, one or more of the reactants must be excited to a higher energy
state as shown in Fig. 5.4. The rate of the forward reaction is controlled by the number of
molecules which possess enough energy to surmount this energy barrier, that is, the rate
Fig. 5.4 The energy profile for the reaction that converts reactants to someproducts via the
transition state

All interactions between elements and compounds are regulated by the free energy changes
available to them. If we denote the net energy change by G, and together with the fact
that natural changes involve transitions from high to low energy levels, then by convention,
we denote energy absorbed by +ve sign, and energy released by –ve sign. Forspontaneous
reaction to occur then G must be –ve.

Question:

Why do gold, platinum and other metals not corrode in wet

aerated environment?

If G is +ve then corrosion is unlikely, and further if the free energy of activation (energy
required to overcome a barrier) is too large, the corrosion rate may be too slow or corrosion
may not proceed.

When a metal atom corrodes, that is, undergoes a corrosion reaction, it is converted into an
ion by a reaction species available in the environment. If we denote the metal by letter M,
then the corrosion can be represented by the equation

M  M Z  Ze (5.1)

where Z = 1, 2, or 3, and is called the valency. High values of Z are quite rare. Equation
(5.1) is the general form of a corrosion reaction. In the above reaction, the metal has been
oxidized.

In the reaction represented by equation (5.1) the principal of electroneutrality must be

conserved. That is, the electrons created must be consumed somewhere, a process
accomplished by generating a negative ion (anion) to balance the +ve ion (MZ+). This is
the reverse process of oxidation, and is known as reduction. For example,

Example:

When nickel (Z = 2) is heated in oxygen (Z= 2) to form nickel oxide, the reaction can be
written as

Ni  Ni 2  2e (oxidation)
(reduction)
O  2e  O2

Ni  O  Ni 2  O2

5.2.1 Factors affecting corrosion

These include:
(i) Temperature of the surrounding;
(ii) The diffusion rates of the reaction products;
(iii) The equilibrium concentration of the ions or reaction products in the solution;
(iv) The pH value of the solution;
(v) Electrolyte velocity
(vi) Solid or dissolved pollutants
(vii) Relative humidity.

Question
Why and how do temperature, and the diffusion rates affect
corrosion?
There different types of corrosion and these are

i) Direct corrosion by dry gases

 ii) Ionization of water (electrochemical corrosion)
This corrosion occurs only in the presence of water or aqueous solutions
and is dependent on the concentration of ions present in the solution.
As a result of slight inhomogeneities in the metal, or inconsistency in ion
concentrations in the electrolyte (solution), local anodic and cathodic
regions will form with the concomitant potential differences between them.
This may in turn lead to localized corrosion occurring on a single piece of
metal.

There are certain salient points we need to know.

1. The anode corrodes by loss of electrons from the metal resulting in
the formation of ions, which may either remain in the solution or
react into an insoluble product. If an insoluble product which
adheres to the surface (anode) is formed, continued dissolution of
the metal is slowed down, if not stopped. The surface of the metal is
then said to be passivated. In other words the surface becomes
passive. You may have noticed this kind of corrosion and
subsequent passivation at the terminals of a car battery.
2. The cathode normally does not undergo corrosion even though it
may suffer damage.
3. The electrolyte is the medium to conduct the electricity registered
by the voltmeter (galvanometer)
4. The electrical conductor connects the anode and the cathode.

5.2.2. Manifestation of corrosion

Corrosion, in particular bimetallic corrosion, manifests itself in different forms. These

are:

(i) Uniform attack-where the entire surface of the metal is corroded uniformly,
(ii) Pitting- a localized corrosion that preferentially attacks areas of metal
surfaces where there is a scratch or broken protective film or compositional
inhomogeneity,
(iii) Crevice corrosion- localized (limited to crevices) in nature initiated by
differential concentration of oxygen or ions in the electrolyte,
(iv) Intergranular corrosion-takes places when the grain boundaries are more
reactive than the rest of the metal especially in alloys,
(v) Stress corrosion-a form of Intergranular corrosion associated with the
simultaneous action a static tensile stress and a specific environment,
(vi) Corrosion fatigue-this the action of corrosion in the presence of cyclic
(repeated) stresses. Corrosion fatigue is highly non-specific, and therefore
a common and highly dangerous form of corrosion.
(vii) Fretting or erosion corrosion- occurs as a result of relative motion between
the electrolyte and a metal surface
5.2.3 Prevention of corrosion/Corrosion control

While corrosion may not be practically prevented, it can be controlled. The most
important ways of control are:

(a) modification of the design particularly controls the geometrical shapes and
structures. Sharp curvatures or processing techniques that increase stress
concentrations are avoided;
(b) modification/control of the environment;
(c) application of inhibitors using particularly materials that will form passive
layers or barrier (protective) coats (e.g. paints);
(d) appropriate selection of materials, e.g., noble metals are more corrosion
resistant, whereas the inert ones are rather expensive, and by avoiding
unnecessary bimetallic corrosion cells or use insulating layers to separate the
different materials;
(e) cathodic and anodic protection
(f) control the pH value to make the solution more alkaline with the effect that the
corroding electrode more passive.

Questions
1. Cite examples where the above methods have beenused
to control/prevent corrosion
2. Why is the presence of corrosion likely to cause
fracture?
3. Define fracture. Explain why steel, which under normal
conditions is ductile is more likely to suffer brittle fracture
rather than ductile fracture when it is cooled to liquid
nitrogen temperature.
4. Discuss the role of oxygen in the corrosion of steel.
5. Explain the mechanism of rust formation beneath adrop
of water on a steel surface.
6. Distinguish between anodic protection and cathodic
protection against corrosion.