Imperfections in the Atomic

Arrangement
 Imperfections in Crystalline Phases
Nothing is perfect.•
Imperfection can be due to:•
Atom in wrong place – missing or foreign atoms
(contamination)

But in some cases:

Some impurities are added to improve the properties of
materials, e.g. Cu is added to Au or Ag to increase the
hardness and durability of the objects.

Zinc when mixed with copper forms brass, an alloy with better
mechanical properties.
 Point Defects
The simplest defects are point defects. e.g. a vacancy, •
due to a missing atom.
Results from imperfect packing during crystallization or •
thermal vibrations at high temperatures, or
2 vacancies combine to form a divacancy or 3 to form tri- •
vacancy
In ceramics vacancies occur in such a way that electro- •
neutrality must be maintained. i.e. whenever a positive
ion is missing, (-ve) ions with a corresponding charge
must be missing too.
The absence of a positive or (-ve) ions from a crystal is •
called Shottky Defect
 Point Defects
When an extra atom is lodged in the crystal in a position •
that does not belong to the crystal lattice, this defect is
called Interstitalcy
When an ion leaves its normal place and lodges itself •
into interstitial site, the compound defect is known as
Frenkel defect (Vacancy + interstitalcy)
 Point Defects

Point Defects. (a) Vacancy, D. (b) Di-vacancy (two missing atoms). (c)
Ion-pair vacancy (Schottky defect). (d) Interstitialcy. (e) Displaced ion
(Frenkel defect).
 Line Defects (Dislocations)
The most common type of line defects is a dislocation. •
An edge dislocation (┴) is shown below. •

Edge Dislocation,  A linear defect occurs at the edge of an extra

plane of atoms. The slip vector b is the resulting displacement.
 Line Defects (Dislocations)
Zones of compression and tension accompany an edge •
dislocation:

Dislocation Energy. Atoms are under compression (dark)

and tension (light) near the dislocation

The dislocation of atoms around the dislocation line is

called Burger’s Vector b
 Line Defects (Dislocations)

Screw Dislocation. The slip vectore (b) is parallel to the

linear defect.

Burger’s vector is parallel to the linear defect. Crystal

growth is facilitated by screw dislocations
 Line Defects (Dislocations)

Dislocation Formation by Shear. (a) The dislocation line. D, expands

through the crystal until displacement is complete. (b) This defect forms a
screw dislocation where the line is parallelto the shear direction. (c) The linear
defect is an edge dislocation where the lineis perpendicular to the shear
direction.
 Grains and Grain boundaries

Surface Atoms (Schematic). These atoms are not entirely surrounded by others, so
they possess more energy than do the internal atoms.
 Grains and Grain Boundaries (Iron,
Grain Boundaries. Note the disorder at X500). Each grain is a single crystal.
the boundary. The
boundaries between grains are
surfaces of mismatch.
Example 4.1
Accurate measurements can be made to four significant figures of the density
of aluminum. When cooled rapidly from 650o C, Al = 2.698 Mg/m3. Compare
that value with the theoretical density obtained from diffraction analyses where
a was determined to be 0.4049 nm.
Procedure: use the method for density determination based on the fact that
aluminum is fcc contains 4 atoms/unit cell.

mass of 4 atoms in the unit cell

 theor 
volume of the unit cell

mass of 4 atoms in the unit cell

 theor  3
(lattice constant)

23
4(26.98 amu)/(6.02 2 x 10 amu/g)
 theor   2.70 Mg/m
3
-9 3
(0.4049 x 10 m)

 2 . 698
  0 . 999 or ~ 1 vacancy per 1000 atoms
 theor 2 . 700
 Noncrystalline Materials
Long range order is absent in some materials of major •
importance
e.g. liquids, glass and Majority of plastics •

Few metals when rapidly cooled form non-crystalline •

solids

Non –crystalline solids are called amorphous solids •

Liquids: fluids (flow under their own mass)

Many liquids of technical importance can become very

viscous and even solids without crystallizing
 Melting of Metals
Providing of heat energy not only results thermal •
vibrations but also vacancies, e.g. Lead

Melting of Metals: (a) Crystalline metals with CN = 12 and (b) Liquid metal.
CN<12
Crystalline lead contains 0.1% vacancies which increase •
to 1% by heating.
This results in destruction of the 12-fold coordination and •
disappearance of the long-range order.
Energy is required to disrupt the crystalline structure •
upon melting. This energy I called the heat of fusion
(Hf).
It differs from one material to another according to the •
following table.
 Melting increases volume of •
most metals and ionic solids
Volume Changes with By melting the CN drops e.g. •
Temperature from 12 to 11 or 10 in fcc and
(Sodium - bcc, Lead - fcc, hcp crystals
Magnesium-hcp). Metals with
In materials with network •
these structures expand on
melting.
structures with stereo-specific
i.e. low PF
e.g. diamond and silicon •
Volume decrease by melting
Volume Changes with Temperature. (a) Ice (hydrogen-bridge bonding). (b) Silicon
(covalently-bonded). The coordination number is low for both bondings. Therefore, the
packing factors of the solids are low. The structures collapse into smaller volumes as they
melt.
 GLASSES
Glasses are very viscous liquids and non-crystalline •
At high temperatures glasses form true liquids and •
respond to shear stress
Thermal contraction is formed by solidification. •
Extensive cooling leads to abrupt change is thermal •
expansion coefficient
Below certain temperature called Glass transition •
temperature or more simply the glass temperature, there
is no further arrangement of the atoms and further
cooling results only in reduction of thermal vibrations
Volume Changes in Supercooled
Liquids and Glasses.
When a liquid is cooled, it contracts rapidly
and continuously because, with decreased
thermal agitation, the atoms develop more
efficient packing arrangements. In the
absence of crystallization, the contraction
continues below Tm to the glass-transition
temperature, Tg, where the material
becomes a rigid glass. Below Tg, no
further rearrangements occur, and the only
further contraction is caused by reduced
thermal vibrations of the atoms in their
established locations.