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CHAPTER 4:

IMPERFECTIONS IN SOLIDS
ISSUES TO ADDRESS...
What types of defects arise in solids?

Can the number and type of defects be varied


and controlled?

How do defects affect material properties?

Are defects undesirable?

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Types are :
Point Defects: Associated with one or two
atom positions
Linear: One dimensional
Interfacial defects or boundaries: Two
dimensional

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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.

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TYPES OF IMPERFECTIONS

Vacancy atoms
Interstitial atoms Point defects
Substitutional atoms

Dislocations Line defects

Grain Boundaries Area defects

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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

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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
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EQUIL. CONCENTRATION: POINT DEFECTS

No. of defects Activation energy

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/at om K)
Each lattice site
is a potential
vacancy site Activation Energy Qv: Energy required
for the formation of a vacancy

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Example 4.1: ESTIMATING VACANCY CONC.

Find the equil. # of vacancies in 1m3 of Cu at 1000C.


Given:

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 = x x 1m3 = 8.0 x 1028 sites
ACu
Answer:
Nv = 2.7 10-4 8.0 x 1028 sites = 2.2x 1025 vacancies
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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
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Impurity Atoms: ALLOYS FORMATION

Solid Solution Substitutional

Interstitial

Solid solution of B in A (i.e., random dist. of point


defects)

OR

Substitutional alloy Interstitial alloy


(e.g., Cu in Ni) (e.g., C in Fe- Steel)
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SOLID SOLUTION
Definitions:
Solvent Host Atoms
Elements or Compounds present in greatest amount
Solute Impurity
An element or compound present in minor concentration
A solid solution forms when, as the solute atom are added to the
host materials the crystal structure is maintained, and no new
structures are formed
A Solid Solution is compositionally homogeneous; the impurity
atoms are randomly and uniformly dispersed within the solid (just
like a liquid solution)
Sometimes addition of impurity atoms results in the formation of
a new phase, that is, no longer a solid solution
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Alloy Formation Due to Impurities
Two outcomes if impurity (B) added to host (A):
SOLID SOLUTION of B in A (i.e., random dist. of point
defects)

OR

Substitutional alloy Interstitial alloy


(e.g., Cu in Ni) (e.g., C in Fe-Steel)
TWO PHASES: (1) Solid solution of B in A plus (2)
particles of a new phase (usually for a larger amount of
B)
Second phase particle
--different composition
--often different structure.
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Hume-Rothery Rules for Alloy Formation
The Hume-Rothery rules are conditions that must be satisfied in
order for unlimited solubility to take place, otherwise multiple
phases may form:
1. Atomic Size factor: *Atomic size should be approximately equal
Atoms may only have a 15% difference in radius, otherwise, the strain on
the lattice will be too great
2. Crystal Structure: *Crystal structure should be same
Each pure components in the alloy must have same crystal structure
3. Electro-negativity: *Electronegativities should be same
Each atoms must have approximately the same electronegativity. Great
differences in electronegativity will encourage the formation of ionic
compounds, not solutions(the tendency of an element to gain an electron)
4. Valences: A metal will have more chances to dissolve another metal of
higher valency than one of a lower valency (almost equal valency favour
solid solution formation)
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Cu-Ni ALLOY:
Cu-Ni alloy is a Substitutional alloy and satisfies all conditions of Hume-
Rothery Rules
Atomic radii of Cu and Ni are 0.128 and 0.125 nm, respectively
Both have FCC crystal structure
Electronegativity of Cu and Ni are 1.9 and 1.8, respectively
Copper has valences of +1 and Nickel +2

Fe-C ALLOY (Steel):


Fe-C alloy is Interstitial alloy
The interstital atom has to be small as compared to host atoms, specially in
close packed crystal structure where there is not enough space
Atomic radius of Carbon is 0.071 nm and Fe 0.124 nm
Normally interstitial atoms can be dissolved to maximum concentration of
10%
The maximum concentration of C in solid solution of Fe-C is 2%
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COMPOSITION
Composition (or Concentration) of an alloy in terms of its
constituent elements
Two common ways to express composition are: (1) Weight or
mass percent (wt%) and (2) Atom percent (at%)

Weight or mass percent (wt%): CA = (mA/mA+mB) x 100


mA and mB are weight of constituent A and B

Atoms percent (at%): Based on calculations of number of


moles of an element in an alloy
CA = (nmA/nmA+nmB) x 100
nmA and nmB are moles of A and B
nmA = mA/A.WA (where is mA mass in grams and A.WA is atomic
weight)
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COMPOSITION
Definition: Amount of impurity (B) and host (A)
in the system.
Two descriptions:
Weight % Atom %

Conversion between wt % and at% in an A-B alloy:


C'BAB
CB = x 100
C'AAA + C'BAB
Basis for conversion:

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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)
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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

Burger vector remains constant along a dislocation line although


the character of line may change from edge to screw
For metallic materials Burgers vector will point in close-packed
crystallographic direction and will be of magnitude equal to an
interatomic spacing
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Edge Dislocation

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Screw Dislocation

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Mixed Dislocation

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Dislocations
Dislocations are line defects that control the plastic deformation of metals

Dislocations are observed by high magnification transmission electron microscopy

Transmission Electron Micrographs of Dislocations


100nm
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Dislocations

A dislocation is a line defect

There are several types of


dislocation character
(edge, screw, mixed)
1m

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Edge Dislocation
Dislocations

1 nm Dislocation

This is an edge dislocation, Distortion of the crystal lattice,


which is equivalent to an extra viewed in a high resolution
half-plane of atoms electron microscope

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Edge Dislocation

An edge dislocation is the line at the


bottom of an extra half-plane of
atoms in the crystal structure.

The line vector is along the line of


the half-plane.
The Burgers vector is the
displacement required to close a
loop of equal atom spacing
disrupted by the half-plane, and is
perpendicular to the line vector.

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Screw Dislocation
A screw dislocation is the line
created by shearing along a plane

The Burgers vector is the


displacement required to close a
loop of equal atom spacing
disrupted by the shear, and is
parallel to the line vector.

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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

DISLOCATIONS ARE IMPORTANT IN PLASTIC


DEFORMAITON OF MATERIALS (including Metals,
Ceramics and Crystalline Polymers):
The extra half plane of atoms (in edge dislocation) moves to produce slip
or permanent plastic deformation

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Dislocations and Slip
Dislocations:
cause slip between crystal plane when they move
produce permanent (plastic) deformation.

Schematic of a Zinc (HCP):


before deformation after tensile elongation

slip steps

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INCREMENTAL SLIP
Dislocations slip planes incrementally...

The dislocation line (the moving red dot)...


...separates slipped material on the left
from unslipped material on the right.

Simulation of dislocation
motion from left to right
as a crystal is sheared.

(Courtesy P.M. Anderson)


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BOND BREAKING AND REMAKING
Dislocation motion requires the successive bumping
of a half plane of atoms (from left to right here)
Bonds across the slipping planes are broken and
remade in succession.

Atomic view of edge


dislocation motion from
left to right as a crystal
is sheared.

(Courtesy P.M. Anderson)

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DISLOCATIONS & CRYSTAL STRUCTURE
Structure: close-packed view onto two
planes & directions close-packed
planes.
are preferred.

Comparison among crystal structures:


FCC: many close-packed planes/directions;
HCP: only one plane, 3 directions;
BCC: none
Results of tensile Mg (HCP)
testing.
tensile direction
Al (FCC)
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Dislocations
Dislocations affect many other properties of materials in
addition to Plastic deformation

The dislocations behaviour depends on their character

Properties affected include


Plastic deformation
Toughness
Electrical and Optical Properties
Diffusion kinetics
Creep
Corrosion
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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

The Interfacial or Area Defects are: External Surfaces, Grain


Boundaries and others

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)

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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
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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
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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
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Grains and Grain Boundaries (4)
The interface between
adjacent crystals or
grains is the grain
boundary.

The grain boundary


has many vacancies

Most metals are polycrystalline


Each grain is a single crystal
The polycrystalline metal may have
texture due to its processing

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Polycrystalline Structure
Grain Formation (5)
Grains result from random
nucleation from liquid
Grain structure in solids can
be modified by deformation
and recrystallization

200 m Nucleation of grains during


solidification of a liquid

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QuickTime Movie
OTHER DEFECTS
OTHER INTERFACIAL DEFECTS:

Twins, Stacking Faults and Phase Boundaries

BULK or VOLUME DEFECTS:

Much larger in size than what have been discussed before


Pores, Cracks, and Foreign Particles
Introduced during processing and fabrication

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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
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Importance of Microscopic Examination
Microscopic examination is important for characterization of
materials due to the following reasons:

To study relationship between properties and structures (and


defects)
To predict properties of materials after the relationship have been
discovered
To design new and better materials based on the structure property
relationship
To determine whether the material has been correctly heat treated
and processed
To find the mode and causes of fracture after failure by observing
the fracture surface

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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

Contrast produced due to differences in reflectivity


of various regions of microstructure

Investigation by optical microscopy is often termed as


METALLOGRAPHY since metals were first examined using this
technique
Used to study the microstructure, fracture surface, relation
between properties and structure, effect of heat treatment etc.
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Metallorgraphy
Investigation by light microscopy is normally termed as
Metallography and consists of the following steps:
Specimen surface is ground and polished to a smooth and mirror
like finish (fine abrasive papers and powders are used for this
purpose)
The polished surface is exposed to an appropriate chemical reagent
by a procedure called ETCHING
Due to different crystal orientation in grains, the chemical reactivity
will be different, and each grain will have different contrast (shade)
due to different amount of material removed
Small grooves will also be created along the grain boundaries: since
atoms are more reactive at the grain boundaries they dissolve at a
greater rate, and the grain boundaries can be observed as dark lines
Different phases can also be observed by proper etching and
subsequent light microscopy
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Optical Microscopy (2)
Useful up to 2000X magnification.
Polishing removes surface features (e.g., scratches)
Etching changes reflectance, depending on crystal
orientation

close-packed planes

micrograph of
Brass (Cu and Zn)

0.75mm
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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.

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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
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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
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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 gr ain 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

n: Grain Size Number


ranges from 1 to 10

Larger the number smaller


the grains
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SUMMARY
Point, Line, and Area defects arise 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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