IMPERFECTIONS IN
CRYSTALS
BY,
MAYUR BAGALE
AND
SUSHANT MODI.
IMPERFECTIONS IN CRYSTALS
ISSUES TO ADDRESS...
• How do defects affect material properties?
• What types of defects arise in solids?
• Are defects undesirable?
Crystalline Imperfections
There is no such thing as a perfect crystal!
• Thermodynamically “impossible”
• “defects” lower the energy of a crystal & make it more stable
• always have vacancies and impurities, to some extent
Defect does not necessarily imply a bad thing
• addition of C to Fe to make steel
• addition of Cu to Ni to make thermocouple wires
• addition of Ge to Si to make thermoelectric materials
• addition of Cr to Fe for corrosion resistance
• introduction of grain boundaries to strengthen materials
…… and so on
“Defect” (in this context) can be either desirable or undesirable.
In general, a defect simply refers to a disruption in the crystalline
order of an otherwise periodic material.
CRYSTALLINE
IMPERFECTIONS are frequently
classified according to geometry or
dimensionality of the defect.
Point defects
Line defects
Interfacial defects
Bulk or volume defects
Point Defects
Atoms in solid possess vibrational energy, some
atoms have sufficient energy to break the bonds
which hold them in eqbm position. Hence once the
atoms are free they give rise to Point Defects.
Classes of point defects:
Intrinsic defects.
1. Vacancy
2. Interstitial
Extrinsic defects
1. Substitution
2. Interstitial
Vacancies
A lattice position that is vacant because the
atom is missing
There are naturally occurring vacancies in
all crystals
The concentrations of vacancies increase
with:
increasing temperature
decreasing activation energy
Vacancies
-vacant atomic sites in a structure.
Vacancy
distortion
of planes
Self-Interstitial
If the matrix atom occupies its own interstitial
site, the defect is called Self Interstitial.
Self-interstitialsin metals introduce large
distortions in the surrounding lattice.
self-
interstitial
distortion
of planes
For Ionic Solids, Frenkel and Schottky
defects are likely to form.
Schottky Defects
When cation vacancy is associated with anion
vacancy, the defect is called Schottky Defect.
Frenkel Defects
When an atom leaves its regular site and
occupy nearby interstitial site it gives rise to two
defects i.e. one vacancy and other self interstitial
these two defects are called as Frenkel Defects.
DEFECTS IN CERAMIC
STRUCTURES
• Frenkel Defect
--a cation is out of place.
• Shottky Defect
--a paired set of cation and anion vacancies.
Shottky
Defect: Adapted from Fig. 13.20,
Callister 5e. (Fig. 13.20 is
from W.G. Moffatt, G.W.
Pearsall, and J. Wulff, The
Structure and Properties of
Materials, Vol. 1, Structure,
Frenkel John Wiley and Sons, Inc., p.
78.) See Fig. 12.21, Callister
Defect 6e.
Q D / kT
• Equilibrium concentration of defects ~ e 8
Equilibrium Concentration:
Point Defects
• Equilibrium concentration varies with temperature!
No. of defects Activation energy
Nv Q v
No. of potential exp
defect sites. N kT
Temperature
Boltzmann's constant
(1.38 x 10 -23 J/atom-K)
(8.62 x 10 -5 eV/atom-K)
Each lattice site
is a potential
vacancy site
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Measuring Activation Energy
• We can get Qv from Nv Q v
an experiment. = exp
kT
N
• Measure this... • Replot it...
Nv Nv slope
ln
N N
- Q v /k
exponential
dependence!
T
1/ T
defect concentration
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Line Defects
Line defects are imperfections in a crystal
structure for which a row of atoms have a
local structure that differs from the
surrounding crystal.
1. Edge dislocations
2. Screw dislocations
Linear Defect (Dislocations)
Are one-dimensional defects around which atoms
are misaligned
Edge dislocation:
◦ extra half-plane of atoms inserted in a crystal
structure
◦ Burger vector to dislocation line
Screw dislocation:
◦ spiral planar ramp resulting from shear
deformation
◦ Berger vector to dislocation line
Edge Dislocation
Screw Dislocation
Interfacial Defects
Are boundaries that have two dimensions
and normally separate regions of the
materials that have different crystal
structures.
1. External surface
2. Grain boundary
3. Twin boundary
External Surfaces
Surface atoms have unsatisfied atomic
bonds, and higher surface energies, γ (J/m2
or, erg/cm2) than the bulk atoms.
To reduce surface free energy, material
tends to minimize its surface areas against
the surface tension (e.g. liquid drop).
Grain Boundaries
Polycrystalline material comprised of many small crystals
or grains having different crystallographic orientations.
Atomic mismatch occurs within the regions where grains
meet. These regions are called grain boundaries.
Segregation of impurities occurs at grain boundary.
Grains tend to grow in size at the expense of smaller grains
to minimize surface energy. This occurs by diffusion, which
is accelerated at high temperatures.
Dislocations can usually not cross the grain boundary.
Twin Boundaries
Special type of grain boundaries with twin
directions mirrored atomic positions across
the boundary.
May be produced by shear deformation of
BCC/HCP materials (mechanical twin), or
during annealing following deformation
(annealing twin) of FCC materials
Bulk or Volume Defects
Pores
affect optical, thermal, and mechanical
properties
Cracks
affect mechanical properties
Foreign inclusions
affect electrical, mechanical, optical
properties
Summary
• Point, Line, and Area defects exist in solids.
• The number and type of defects can be varied
and controlled (e.g., T controls vacancy conc.)
• Defects affect material properties (e.g., grain
boundaries control crystal slip).
• Defects may be desirable or undesirable
(e.g., dislocations may be good or bad, depending
on whether plastic deformation is desirable or not.)
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THE END
