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Chapter 4
Chapter 4
IMPERFECTIONS IN SOLIDS
ISSUES TO ADDRESS...
• What types of defects arise in solids?
1
Introduction
• Perfect order at atomic level does not exist in real crystalline solids
All contains large number of various defects or imperfections
• Many properties vary due to presence of theses defects (and some
properties are very sensitive to the presence of defects)
• DEFECTS are not always “BAD” and are sometimes introduced
deliberately
• Crystalline Defects Lattice Irregularity with one or more of its
dimensions of the order of an atomic diameter.
• Types are:
– Point Defects: Associated with one or two atom positions
– Linear: One dimensional
– Interfacial defects or boundaries: Two dimensional
2
TYPES OF IMPERFECTIONS
• Vacancy atoms
• Interstitial atoms Point defects
• Substitutional atoms
3
POINT DEFECTS: Pure Materials
Vacancies and Self Interstitials
• Vacancies:
-vacant atomic/lattice sites in a structure.
Vacancy
distortion
of planes
• Self-Interstitials:
-"extra" atoms positioned between atomic sites.
self-
distortion interstitial
of planes
4
Vacancies
• All crystalline solids contains vacancies It is impossible
to make atoms free of these defects
• The necessity of the presence of vacancies is explained by
the principles of thermodynamics
• Equilibrium concentration of vacancies increases with
temperature The relation is exponential
• For most metals, the fraction of vacancies Nv/N just below
melting temperature is of order of 10-4 (one lattice site out of
10,000 is empty)
• If N is the total number of atomic sites, Qv is the energy
required for the formation of vacancy (Activation Energy),
the equilibrium number of vacancies Nv is given by the
equation on the next slide
5
EQUIL. CONCENTRATION: POINT DEFECTS
Nv = -Q
exp
v
N kT
No. of potential Temperature
defect sites. 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 Activation Energy Qv: Energy required
for the formation of a vacancy
6
Example 4.1: ESTIMATING VACANCY CONC.
0.9eV/atom
Nv = -Q
exp
v = 2.7 · 10-4
N kT
1273K
8.62 x 10-5 eV/atom-K
NA
For 1m 3, N = r x x 1m3 = 8.0 x 1028 sites
ACu
• Answer:
Nv = 2.7 · 10-4 · 8.0 x 1028 sites = 2.2x 1025 vacancies
7
Impurities in Solids
• It is impossible to have a 100% pure materials (with only one type
of atoms) Impurity or Foreign atoms always present
• 99.9999% pure will still have 1022 to 1023 impurity atoms in 1 m3
of material
• In Alloys, impurity atoms are intentionally added to impart
specific characteristics to materials such as improved mechanical
strength and corrosion resistance
• Addition of impurity atoms to metals will result in the formation
of SOLID SOLUTION (just like a liquid solution) and/or a new
SECOND PHASE
• The presence of solid solution or second phase depends on the
kinds of impurity, their concentration and temperature
• Impurity atoms Solute; Host atoms Solvents
8
Impurity Atoms: ALLOYS FORMATION
Interstitial
OR
OR
15
Example 4.3
LINE DEFECTS: DISLOCATIONS
• A dislocations is a linear or one-dimensional defect around which
some of the atoms are misaligned.
• Types of Dislocations are: Edge, Screw and Mixed Dislocations
• EDGE DISLOCATION:
– A extra-half-plane of atom is added within crystal
– End of the extra half plane is a line defect: Lattice is distorted
along that line Dislocation Line
– Within the region around dislocation line there is some
localized lattice distortion
– Atoms above dislocation line are squeezed together and those
below are pulled apart
– Some times edge dislocation line is represented by symbol
(also indicate position of the dislocation line)
16
17
DISLOCATIONS (Contd.)
• SCREW DISLOCATION:
– The upper region is shifted by distortion of one atom distance relative to
bottom portion (can be thought to be produced because of shearing of
planes)
– Present in the form of spiral or helical path (the atomic panes trace a helical
path around dislocation line): Represented by a semicircle arrow
• MIXED DISLOCATION:
– Mostly dislocations are mixed; they have the characteristics of both edge
and screw dislocations
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Burgers Vector
• The magnitude and direction of lattice distortion associated with
dislocations is expressed by burgers vector b
• Nature of dislocation is defined by the relative orientations of
dislocation line and Burger vector
– For an edge dislocation the burgers vector is perpendicular to the
dislocation line
– For a screw dislocation the burgers vector is parallel to the dislocation line
– For mixed dislocation they are neither perpendicular nor parallel
20
Screw Dislocation
21
Mixed Dislocation
22
Dislocations
• Dislocations are line defects that control the plastic deformation of metals
24
Edge Dislocation
• Dislocations
1 nm Dislocation
25
Edge Dislocation
26
Screw Dislocation
• A screw dislocation is the line
created by shearing along a plane
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DISLOCATIONS (Contd.)
• All crystalline materials contains dislocations:
• Sources of Dislocations include:
1. Solidification
2. Plastic Deformation
3. Due to thermal stresses due to rapid cooling
4. Grain Boundaries
5. Many more
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Dislocations and Slip
Dislocations:
• cause slip between crystal plane when they move
• produce permanent (plastic) deformation.
slip steps
29
INCREMENTAL SLIP
• Dislocations slip planes incrementally...
Simulation of dislocation
motion from left to right
as a crystal is sheared.
31
DISLOCATIONS & CRYSTAL STRUCTURE
• Structure: close-packed view onto two
planes & directions close-packed
planes.
are preferred.
33
INTERFACIAL OR AREA DEFECTS
• Interfacial defects are boundaries having two dimensions (area or
plane) separating regions of materials that have different crystal
structures and/or crystallographic orientations
• EXTRENAL SURFACES:
– A defect since the periodic three dimensional arrangement is disturbed (the
crystal structure terminates)
– The surface atoms are not bound to maximum number of nearest atoms and
are therefore in high energy state
– Extra energy quantified as surface energy
– Materials tend to reduce this energy by decreasing surface area (e.g: water
droplet)
34
• GRAIN BOUNDARIES:
– A boundary separating two small grains
or crystals having different orientations in
a polycrystalline materials
– Boundary is few atoms thick and
accommodates the mismatch in
orientation from one crystalline
orientation to another
– The grain boundary angle quantifies
mismatch in orientation (small angle
smaller mismatch)
– Smaller mismatch produces small or low
angle grain boundary
– Grain boundaries are high energy sites
and therefore ETCH (chemically react)
more readily to show the microstructure
35
Grain Boundaries (2)
• The atoms near the grain boundaries do not generally have a periodic
structure.
• They are high energy sites (like external surfaces) with a more open
structure than the crystal structure in the grains
• The amount of interfacial or grain boundary energy depend on the
degree of misorientation
• Grain boundaries ETCH (Chemically React) more readily to show
microstructure due to the presence of extra energy
• Grain boundaries can have important effects on the properties of
materials
– Alloying elements and impurities tend to segregate to grain boundaries.
This may cause embrittlement or localised corrosion
– Grain boundaries can act as easy diffusion paths, encouraging creep failure
– Precipitates are often nucleated at grain boundaries, this may also cause
embrittlement or localised corrosion, and can either reduce or improve the
creep resistance 36
GRAIN BOUNDARIES (3)
Grain boundaries:
• are boundaries between crystals.
• are produced by the solidification process, for example.
• have a change in crystal orientation across them.
• impede dislocation motion.
Metal Ingot
Schematic ~ 8cm
grain
boundaries
heat
flow 37
Grains and Grain Boundaries (4)
• The interface between
adjacent crystals or
grains is the grain
boundary.
38
Polycrystalline Structure
Grain Formation (5)
• Grains result from random nucleation
from liquid
• Grain structure in solids can be
modified by deformation and
recrystallisation
39
QuickTime Movie
OTHER DEFECTS
• OTHER INTERFACIAL DEFECTS:
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MICROSCOPIC EXAMINATION
• It is important to examine the structural elements and defects that
influence the properties of materials
• Such as, the SHAPE and AVERAGE SIZE or DIAMETER of the
GRAINS for a polycrystalline specimen are important MICRO-
STRUCTURAL characteristics
• Grains can be of:
– Macroscopic dimensions Observed by Naked Eye
– But they are mostly of microscopic dimensions (diameter of the order of
few microns) observed only by microscope
Microscopy Optical
Electron
Scanning Probe
41
Importance of Microscopic Examination
• Microscopic examination is important for characterization of
materials due to the following reasons:
42
OPTICAL MICROSCOPY (1)
• A Light Microscope is used to study the microstructure
• Optical and Illumination systems are its basic elements
• For opaque material (like metals and ceramics) only surface can
be studied in Reflective Mode
close-packed planes
micrograph of
Brass (Cu and Zn)
0.75mm
45
Optical Microscopy (3)
Grain boundaries...
• are imperfections,
• are more susceptible
to etching; dissolve at
faster rate
• may be revealed as
dark lines,
• change direction in a
polycrystal.
46
ELECTRON MICROSCOPY
• Capable of higher magnification than Optical Microscopy and thus used for
studying fine features
• Beam of Electron is used instead of Light Radiation
• Wavelength of an electron beam is inversely proportional to velocity of the
electrons
• Wavelength of the order of 0.003 nm can be obtained by accelerating electrons
by high voltage
• Magnetic lenses are used instead of optical lenses
• TYPES OF ELECTRON MICROSCOPY ARE: Transmission Electron
Microscopy, Scanning Electron Microscopy and others
1. Transmission Electron Microscopy (TEM):
– Electron beam passes through thin foil specimen
– Contrast in the image produced by differences in beam scattering or diffraction
produced between various elements of the microstructure or defect
– Dislocations can be seen through TEM
– Magnification 1,000,000x
47
ELECTRON MICROSCOPY (Contd.)
2. Scanning Electron Microscopy (SEM):
– Surface of specimen scanned, and the reflected beam collected and displayed on a
cathode ray tube (like monitor)
– Electrically conductive samples required
– Surface features can be observed with higher depths of fields
– Magnification: 50,000x
3. Scanning Probe Microscopy (SPM):
– A tiny probe with a very sharp tip is brought close (to the order of a nanometer) to
the specimen surface
– During scanning the probe experiences deflections in response to electronic or
other interactions between the probe and specimen surface (its atoms and surface
features)
– Three dimensional topographical map on an atomic scale is generated representing
surface features and characteristics of the specimen
– Magnification 109x
– Atomic Force Microscopy (AFM) an example
– The new SPMs allow examination of the surface of the materials at the atomic and
molecular level
48
Grain Size Determination
• The properties of polycrystalline materials strongly depend on their grain size
• Number of techniques available to measure the average grain volume,
diameter or area
1. Intercept Method: Straight line of same length are drawn on several
micrographs. The grain intersected by the line are counted; the line length is
then divided by average number of grains intersected. The average grain
diameter is found by dividing this result with magnification of micrographs
2. ASTM Method: Micrographs at magnification of 100x are taken. The
number of grains are counted in one in2, and grain size number is assigned by
the formula given below. Standard charts are available and grain size number
can be find by only comparing of the chart with the micrograph
50