Fundamentals Unit 2

 Crystal Defects:

o What to atoms do? o Why do materials have different properties ?

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Fundamentals Unit 2

 Crystal Defects:
oCrystals are rarely perfect. They contain large number of defects
(imperfections) which influence the behaviour of metals.

oBecause of theses defects, the actual strength of the metal is much

less than theoretical values. They are solid at ordinary temperatures,

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Fundamentals Unit 2

 Crystal Defects:

No SOLID is Perfect, every solid has defects or imperfections.

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Fundamentals Unit 2

 Crystal Defects: Colour of Diamonds

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 Fundamentals Unit 2

 Crystal Defects: o Colour of diamonds

C + Si = Green (& even small amount of electrons)

C + B = Blue (& even small amount of electrons) 5

 Fundamentals Unit 2

 Crystal Defects: o Colour of diamonds

C + N2 = Yellow, orange to brown Diamonds

Pure Carbon (just a defect by

plastic deformation)
Red & Pink Diamonds
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 Fundamentals Unit 2

 Crystal Defects: o Colour of diamonds

C + Graphite = Black Diamonds (traces of Fe)

C + H2 leads to Violet/ purple

colored Diamonds

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 Fundamentals Unit 2

 Crystal Defects: Classification of Defects

Crystal Defects

Point Defects Line Defects Surface Defects Volume Defects

1) Vacancy 1) Edge Dislocation 1) Stacking Fault

a) Schottky 2) Screw Dislocation 2) Grain Boundaries
b) Frankel 3) Twinned Boundaries
2) Interstitial
3) Substitutional
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Crystal Defects Unit 2

 Point Defects:

 Point defects are highly localised.

 They involve disruption of lattice involving one or just few atoms.
 Often regarded as zero dimensional defects.
 There are three types of point defects:

1) Vacancy Defect
a) Schottky Defect
b) Frankel Defect
2) Interstitial Defect
3) Substitutional Defect
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Crystal Defects Unit 2

 Point Defects: Vacancy Defect

 Vacancy occurs as a result of atom missing from a normal site.

STM image of a Pt surface. Vacancies are

clearly visible 10
Courtesy of Kiel University, Germany
 Crystal Defects Unit 2

 Point Defects: Vacancy Defect

 These are often caused due to

imperfect packing during original
crystallization or may arise due
to phonon transition (thermal
vibration) of atoms at elevated
temperature.
 Shown by ionic solids
 Normally created when mtl. is
heated
 Results in the decrease of
density STM image of a Si surface. Vacancies are
clearly visible
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Courtesy of Kiel University, Germany
 Crystal Defects Unit 2

 Point Defects: Vacancy Defect

 The concentration of vacancies is important in determining the amount

of diffusion that occurs in solids.

 Vacancy concentration increase with increase in temperature.

 No. of vacancies at given temperature (Nv) are given by:

Where,
N = Total number of atomic sites,
Qv = Energy required for the formation of a
vacancy,
T = Absolute temperature in kelvin, and
k = The Gas or Boltzmann’s constant
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= 1.38 x 1023 J/atom K
 Crystal Defects Unit 2

 Point Defects: Vacancy Defect (example)

 Calculate the equilibrium number of vacancies per cubic meter for copper at
1000 oC. The energy for vacancy formation is 0.9 eV/atom; the atomic weight
and density (at 1000 oC) for copper are 63.5 g/mol and 8.4 g/cm3,
respectively.

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 Crystal Defects Unit 2

 Point Defects: Vacancy Defect (example)

 Calculate the equilibrium number of vacancies per cubic meter for copper at
1000 oC. The energy for vacancy formation is 0.9 eV/atom; the atomic weight
and density (at 1000 oC) for copper are 63.5 g/mol and 8.4 g/cm3,
respectively.

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 Crystal Defects Unit 2

 Point Defects: Vacancy Defect (Schottky Defect)

 Are found in compounds which must maintain charge balance.

 In Schottky defect, the removal of positive ion (to create vacancy)
must be counter balanced by the removal of negative ion in order to
maintain neutrality.

Animated representation of Schottky

defect

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Courtesy of Kiel University, Germany
 Crystal Defects Unit 2

 Point Defects: Vacancy Defect (Schottky Defect)

 The pair of vacancies caused by removal of both positive &
negative ions are called Schottky defect.

 Equal No. of + ve & -ve ions will

be missing, maintaining electric
neutrality
 Common in ionic solids with
similar sized cations and anions
like NaCl, KCl, CsCl e.t.c

 In NaCl there are ~ 106 schottky

pairs /cm3 @ room temperature.

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Courtesy of www.edufine.net
 Crystal Defects Unit 2

 Point Defects: Vacancy Defect (Frankel Defect)

 If an ion is displaced from the normal lattice point to an interstitial

site, then the defect is known as Frankel Defect (also called as self
interstitial defect).

Animated representation of
Frankel defect

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Courtesy of wikimedia.com
 Crystal Defects Unit 2

 Point Defects: Vacancy Defect (Frankel Defect)

 Usually shown in ionic solids containing differences in the sizes of ions

 Normally created when the smaller

ion (usually cation) is dislocated
from its normal site to an
interstitial site.

 Creates a vacancy defect and

interstitial defect.

 AgCl, AgBr, AgI & ZnS e.t.c are

examples…

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Courtesy of wikimedia.com
 Crystal Defects Unit 2

 Point Defects: Vacancy Defect (Schottky & Frankel Defect)

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Courtesy of www.majordifferences.com
Crystal Defects Unit 2

 Point Defects: Impurities in Solids

 A Pure metal consisting of only one type of atom just is not possible.
 Impurity or foreign atoms will always be present, and some will exist
as crystalline point defects.
 Even with the most state of the art and sophisticated techniques, it is
difficult to refine metals with purity in excess of 99.9999%.

 At this level, on the order of 1022 to 1023 impurity atoms will be

present in one cubic meter of metal.
 Most familiar metals are not highly pure, they are Alloys (in which
impurity atoms are added intentionally).

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Crystal Defects Unit 2

 Point Defects: Impurities in Solids

 They are called solid solutions, where we have solvent and solute.
 Solvent is the element/ compound which is in major proportion and
solute is the one is smaller proportion.

 Impurity point defects are

found in solid solutions, of
which there are two types:
a) Substitutional
b) Interstitial.

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 Crystal Defects Unit 2

 Point Defects: Interstitial Defect

 Interstitial defects are formed when an extra atom is inserted into the
lattice at a normally unoccupied site (interstices).

 Such atoms may be impure or by deliberately alloying element.

Animated representation of
Interstitial defect
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Courtesy of www.meritnation.com
 Crystal Defects Unit 2

 Point Defects: Substitutional Defect

 Substitutional defect occurs when one atom in a lattice is replaced

(substituted) by the different atom which may be impurity or
deliberate alloying element.

 Such Substitutional atom can be

smaller or larger than the original
atom.

Animated representation of
substitutional defect

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Courtesy of www.wikipedia.com
 Crystal Defects Unit 2

 Point Defects: Substitutional Defect

For the substitutional type, solute or impurity atoms replace or
substitute for the host atoms. Several features of the solute and solvent
atoms determine the degree to which the former dissolves in the latter, as
follows:

1. Atomic Size Factor,

2. Crystal Structure,
3. Electro-negativity,
4. Valances.

Animated representation of
substitutional defect
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Courtesy of www.wikipedia.com
 Crystal Defects Unit 2

 Point Defects: Overview of Point defects

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Courtesy of www.wikipedia.com
 Crystal Defects Unit 2

 Line/ Linear defects: (Miscellaneous Imperfections)

 Line defects are one dimensional defects and extend along same direction.
 The most common line defect within crystal is dislocation
 Dislocations may be produced during crystallization, but more
commonly originate during deformation.
 They are most significant defects which reduces the strength of the
materials.
 Compared to perfect lattice, a slip plane containing dislocation
requires less shear stress to allow slip. Dislocations are classified as:

1. Edge Dislocations,  Both edge and screw dislocations

may occur together in the crystal
2. Screw Dislocations. forming a mixed dislocations

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 Crystal Defects Unit 2

 Line defects: (Edge Dislocations)

 Edge Dislocation can be described as lattice distortion at the edge of an
extra plane of atoms within the crystal structure.

Origin of the
Edge Dislocation

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 Crystal Defects Unit 2

 Line defects: (Edge Dislocations)

 If the extra plane is above slip plane, the edge dislocation is called +ve
and is represented by symbol

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 Crystal Defects Unit 2

 Line defects: (Edge Dislocations)

 If the extra plane is below slip plane, the edge dislocation is called -ve
and is represented by symbol

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 Crystal Defects Unit 2

 Line defects: (Burgers Vector)

 The displacement distance for atoms around dislocation is called

Burgers Vector.

 It is a measure of
magnitude and direction
of slip due to dislocation
motion.

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 Crystal Defects Unit 2

 Line defects: (Screw Dislocations)

 In screw dislocation, the atoms are displaced in two different planes

perpendicular to each other.

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 Crystal Defects Unit 2

 Line defects: (Screw Dislocations)

 The lattice points trace a helical path around the dislocations, hence the
name screw dislocation

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 Crystal Defects Unit 2

 Line defects: (Screw Dislocations)

 In screw dislocation, Burgers Vector is parallel to the dislocation line

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Crystal Defects Unit 2

 Line defects: (Edge & Screw Dislocations)

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 Crystal Defects Unit 2

 Surface Defects (or) Interfacial Defects:

 Surface imperfections are two dimensional defects, and are the region
of disturbance of few atomic diameters.
 Surface Imperfections (Interfacial defects) can be classified as:

1. Stacking Fault,

2. Grain Boundaries,

3. Twinned Boundaries.

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 Crystal Defects Unit 2

 Surface Defects: Stacking Fault

 Stacking fault results due to breaking the stacking sequence of atomic

planes.

 There will be a atomic plane missing from the normal sequence.

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 Crystal Defects Unit 2

 Surface Defects: Stacking Fault

 For example: the normal sequence of stacking atomic planes in FCC
crystal is …. A C B A C B A C B….

In the plane C is missing from

the above sequence, than the
atomic stacking becomes: ….

A C B A B A C B…. 37
 Crystal Defects Unit 2

 Surface Defects: Stacking Fault

 The stacking sequence due to missing is altered. This surface
imperfection is called stacking fault.

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Stacking fault in the ZnS nanocrystals Courtesy of www.intechopen.com
 Crystal Defects Unit 2

 Surface Defects: Twinned Boundaries

 Twin boundaries constitute a pair and the region between them is twinned
plane. Quartz

Aragonite

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Pseudo hexagonal Twinning
 Crystal Defects Unit 2

 Volume Defects:
 Volume defects such as cracks and porosity may arise in crystals when
there is only small electrostatic dissimilarity between the stacking
sequences of close packed planes in metals.

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 Crystal Defects Unit 2

 Volume Defects:

 Foreign particle inclusions and non crystalline

regions which have the dimensions of the order of

0.20 nm are also called as volume imperfections.

 The accumulation of vacancies produce voids,

while the foreign atoms produce dissymmetry
within crystals. These defects affect properties of
metal.

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 Crystal Defects Unit 2

 Atomic Vibrations: (Phonon)

 Every atom in a solid material is vibrating very rapidly about its lattice
position. This behavior is considered a defect/ imperfection.

 At any given instant of time, not

all the atoms vibrate with same
frequency and amplitude nor
with the same energy.

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 Crystal Defects Unit 2

 Atomic Vibrations:

 With the rise in temperature, there will be rise in average energy.

 Temperature of solid is really just a measure of the average vibrational
activity of atoms and molecules.

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 Crystal Defects Unit 2

 Atomic Vibrations:

 Vibration has a frequency of ~1013/sec, amplitude ~10-11M.

 Most of the properties and processes in solids are manifestations of this
vibrational atomic motion.
 Melting occurs when the vibrations are vigorous and large enough to
rupture large number of atomic bonds.

https://upload.wikimedia.org/wikipedia/comm
ons/9/9b/1D_normal_modes_%28280_kB%29.
gif
https://upload.wikimedia.org/wikipedia/comm
ons/6/6d/Translational_motion.gif

https://en.wikipedia.org/wiki/Equipartition_th
eorem#mediaviewer/File:Thermally_Agitated_
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Molecule.gif