MIRPUR UNIVERSITY OF SCIENCE AND TECHNOLOGY (MUST), MIRPUR

DEPARMENT OF MECHANICAL ENGINEERING

 Imperfections in Solids
(Lecture # 09)
CLO PLO
1 1

Engr. Syeda Iram Zahra

( Lecturer)

BME-122 Engineering Materials 2

 Outline

• Imperfections in solids

• Types of Crystal imperfections

• Point Defects

• Point Defects

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 Imperfections in solids

• The arrangement of the atoms or ions in engineered materials contains imperfections

or defects. These defects often have a profound effect on the properties of materials.

• The natural crystals are not always perfect and there are some deviations
from their regular arrangement. In natural crystals there are some missing
atoms or lattice imperfections.

• Any deviation in a natural crystal from the regular and periodic arrangement
of atoms is known as Crystal Imperfection.

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 Imperfections in solids

In the processing/structure/properties/performance scheme, reasons for

studying imperfections in solids are as follows:
• For the processing of silicon as a semiconducting material, it is important to
specify impurity concentration in appropriate units.
• Development of the desirable mechanical properties for steel alloys relies on
the presence of specific impurities, some of which form solid solutions. Thus, an
understanding of the concept of a solid solution is important.
• The mechanisms of hardening and strengthening for steel alloys involve a
crystalline defect called a dislocation.

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 Imperfections in solids
• There are three basic types of Crystal imperfections :

• point defects,
• line defects (or dislocations),
• surface defects.

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 Imperfections in solids
• These imperfections only represent defects in or deviations from the perfect or ideal
atomic or ionic arrangements expected in a given crystal structure. The material is
not considered defective from a technological viewpoint. In many applications, the
presence of such defects is useful.
• There are a few applications, though, where we strive to minimize a particular type
of defect. For example, defects known as dislocations are useful for increasing the
strength of metals and alloys; however, in single crystal silicon, used for
manufacturing computer chips, the presence of dislocations is undesirable.
• Often the “defects” may be created intentionally to produce a desired set of
electronic, magnetic, optical, or mechanical properties. For example, pure iron is
relatively soft, yet, when we add a small amount of carbon, we create defects in the
crystalline arrangement of iron and transform it into a plain carbon steel that exhibits
considerably higher strength.

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 Imperfections in solids
• Similarly, a crystal of pure alumina is transparent and colorless, but, when we add a
small amount of chromium, it creates a special defect, resulting in a beautiful red
ruby crystal.

• In the processing of Si crystals for microelectronics, we add very small concentrations of P or

B atoms to Si. These additions create defects in the arrangement of atoms in silicon
that impart special electrical properties to different parts of the silicon crystal.
• This, in turn, allows us to make useful devices such as transistors—the basic building
blocks that enabled the development of modern computers and the information
technology revolution.
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 Imperfections in solids
• The effect of point defects, however, is not always desirable. When we want to use
copper as a conductor for microelectronics, we use the highest purity available. This
is because even small levels of impurities will cause an orders of magnitude increase
in the electrical resistivity of copper!
• Grain boundaries are regions between different grains of a polycrystalline material,
and represent one type of defect. Ceramic superconductors, under certain conditions,
can conduct electricity without any electrical resistance.

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 Imperfections in solids
• Materials scientists and engineers have made long wires or tapes of such materials.
They have also discovered that, although the current flows quite well within the
grains of a polycrystalline superconductor, there is considerable resistance to the flow
of current from one grain to another—across the grain boundary.
• On the other hand, the presence of grain boundaries actually helps strengthen
metallic materials.

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 Point Defects

• Point defects are localized disruptions (disturbance) in perfect atomic or

ionic arrangements in a crystal structure.
• Although we call them point defects, this disruption affects a region involving
several atoms or ions.
• These imperfections may be introduced by movement of the atoms or ions
when they gain energy by heating, during processing of the material, or by
the intentional or unintentional introduction of impurities.
• An important “point” about point defects is that although the defect occurs at
one or two sites, their presence is “felt” over much larger distances in the
crystalline material.

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 Point Defects

• Typically, impurities are elements or compounds that are present from raw materials
or processing. For example, silicon crystals grown in quartz crucibles contain oxygen
as an impurity.
• Dopants, on the other hand, are elements or compounds that are deliberately added,
in known concentrations, at specific locations in the microstructure, with an intended
beneficial effect on properties or processing.
• In general, the effect of impurities is deleterious, whereas the effect of dopants on the
properties of materials is useful. Phosphorus (P) and boron (B) are examples of
dopants that are added to silicon crystals to improve the electrical properties of pure
silicon (Si).

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 Point Defects

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 Point Defects

Point defects are usually in the form of :

• Vacancy atoms
• Interstitial atoms
• Substitutional atoms

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 Point Defects
Vacancy atoms A vacancy is produced when an atom or an ion is missing from
its normal site in the crystal structure

• When atoms or ions are missing (i.e., when vacancies are present), the
overall randomness or entropy of the material increases, which increases the
thermodynamic stability of a crystalline material.
• All crystalline materials have vacancy defects.

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 Point Defects
Vacancy atoms
• Vacancies are introduced into metals and alloys during solidification, at high
temperatures, or as a consequence of radiation damage.
• Vacancies play an important role in determining the rate at which atoms or
ions move around or diffuse in a solid material, especially in pure metals.
• At room temperature (298 K), the concentration of vacancies is small, but the
concentration of vacancies increases exponentially as the temperature
increases, as shown by the following Arrhenius type behavior:

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 Point Defects
Vacancy atoms

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 Point Defects

Vacancy atoms
• Due to the large thermal energy near the melting temperature, there may be
as many as one vacancy per 1000 atoms.
• The above equation (a) provides the equilibrium concentration of vacancies
at a given temperature.
• It is also possible to retain the concentration of vacancies produced at a high
temperature by quenching the material rapidly.
• Thus, in many situations, the concentration of vacancies observed at room
temperature is not the equilibrium concentration predicted by Equation (a)

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 Point Defects

Vacancy atoms

Example problem 1:
Calculate the concentration of vacancies in FCC copper at room temperature (25°C).
What temperature will be needed to heat treat copper such that the concentration of
vacancies produced will be 1000 times more than the equilibrium concentration of
vacancies at room temperature? Assume that 20,000 cal are required to produce a
mole of vacancies in copper.
The lattice parameter of FCC copper is 0.36151 nm.
R = 1.98

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 Point Defects

Vacancy atoms Example problem 1: Solution:

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 Point Defects

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 Point Defects

Vacancy atoms

Home Work:

Example problem 2:
Calculate the theoretical density of iron, and then determine the number of vacancies
needed for a BCC iron crystal to have a density of 7.874 g/cm3 . The lattice parameter
of iron is 2.866 x 10-8 cm.
Atomic mass of iron = 55.847 g/mol

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 Point Defects

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 Point Defects
(Lecture # 10)
CLO PLO
1 1

Engr. Syeda Iram Zahra

( Lecturer)

BME-122 Engineering Materials 24

 Outline

• Sub types of point defects

• Interstitial Defects
• Substitutional defect
• Interstitialcy
• Frenkel defect
• Schottky defect

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 Point Defects
Interstitial Defects An interstitial defect is formed when an extra atom or ion
is inserted into the crystal structure at a normally unoccupied position

• Interstitial atoms or ions, although much smaller than the atoms or ions
located at the lattice points, are still larger than the interstitial sites that they
occupy; consequently, the surrounding crystal region is compressed and
distorted.
• Interstitial atoms such as hydrogen are often present as impurities, whereas
carbon atoms are intentionally added to iron to produce steel.
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 Point Defects

Interstitial Defects

• For small concentrations, carbon atoms occupy interstitial sites in the iron
crystal structure, introducing a stress in the localized region of the crystal in
their vicinity.
• The introduction of interstitial atoms is one important way of increasing the
strength of metallic materials.
• Unlike vacancies, once introduced, the number of interstitial atoms or ions in
the structure remains nearly constant, even when the temperature is
changed.

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 Point Defects

Substitutional Defects
• A substitutional defect is introduced when one atom or ion is replaced by a different type of
atom or ion.

• The substitutional atoms or ions occupy the normal lattice site.

• Substitutional atoms or ions may either be larger than the normal atoms or ions in the
crystal structure, in which case the surrounding interatomic spacings are reduced, or
smaller causing the surrounding atoms to have larger interatomic spacings. In either case,
the substitutional defects disturb the surrounding crystal.
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 Point Defects
Substitutional Defects
• The substitutional defect can be introduced either as an impurity or as a deliberate
alloying addition, and, once introduced, the number of defects is relatively
independent of temperature.
• The substitutional atoms will often increase the strength of the metallic material.
• Example: Examples of substitutional defects include incorporation of dopants such as
phosphorus (P) or boron (B) into Si.
• Similarly, if we add copper to nickel, copper atoms will occupy crystallographic sites
where nickel atoms would normally be present.

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 Point Defects

Substitutional Defects
• Example: Substitutional defects also appear in ceramic materials. For example,
if we add MgO to NiO, Mg+2 ions occupy Ni+2 sites, and O-2 ions from MgO
occupy O-2 sites of NiO.

• Whether atoms or ions go into interstitial or substitutional sites depends upon

the size and valence of these guest atoms or ions compared to the size and
valence of the host ions
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 Other Point Defects

Interstitialcy
• An interstitialcy is created when an atom identical to those at the normal lattice
points is located in an interstitial position.
• These defects are most likely to be found in crystal structures having a low
packing factor

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 Other Point Defects

Frenkel defect
• A Frenkel defect is a vacancy-interstitial pair formed when an ion jumps from a
normal lattice point to an interstitial site, leaving behind a vacancy.

• Although, this is usually associated with ionic materials, a Frenkel defect can
occur in metals and covalently bonded materials.
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 Other Point Defects

Schottky defect
• A Schottky defect is unique to ionic materials and is commonly found in many
ceramic materials.
• To maintain the charge neutrality, remove 1 cation and 1 anion from regular atomic
position; this creates 2 vacancies.

• For example, one Mg+2 vacancy and one O-2 vacancy in MgO constitute a Schottky
pair.
• In ZrO2, for one Zr+4 vacancy, there will be two O-2 vacancies
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 Other Point Defects
• An important substitutional point defect occurs when an ion of one charge replaces
an ion of a different charge. This might be the case when an ion with a valence of +2
replaces an ion with a valence of +1.

• In this case, an extra positive charge is introduced into the structure. To maintain a
charge balance, a vacancy might be created where a +1 cation normally would be
located. Again, this imperfection is observed in materials that have pronounced ionic
bonding

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 Other Point Defects

• Thus, in ionic solids, when point defects are introduced, the following rules have to
be observed:

(a) a charge balance must be maintained so that the crystalline material as a whole is

electrically neutral;
(b) a mass balance must be maintained; and
(c) the number of crystallographic sites must be conserved.

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THANKS