Ch4 Imperfections in Solids 2015

9/27/2015
9:43 PM
Chapter 4
Imperfections
in Solids
Mohammad Suliman Abuhaiba, Ph.D.,
1 PE
2 9/27/2015 9:43 PM
Home Work Assignment

1,4, 6, 11, 16, 25, 27, 32, 35,
39, 47
Due Tuesday 6/10/2015
Quiz: Sunday 11/10/2015
Mohammad Suliman Abuhaiba, Ph.D., PE

3 9/27/2015 9:43 PM
Why Study Imperfections in Solids?

Properties of materials are
affected by presence of
imperfections
Crystalline defect: a lattice
irregularity having one or more
of its dimensions in the order of
an atomic diameter
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Types of Imperfections
Imperfections are Classified
according to geometry or
dimensionality of the defect.
3 basic types of imperfections:
1. Point defects (PD)
2. Line defects (dislocations)
3. Surface defects, SD
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Point Defects (PD)

 Localized disruptions in otherwise perfect
atomic or ionic arrangement in a crystal.
 Imperfectionsintroduced by movement of
atoms or ions when they gain energy:
 by heating
 during processing
 by introduction of impurities
 doping
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Point Defects (PD)

 Impurities:
elements or compounds that is
present from raw materials or processing
 Dopants:
 Elements or compound deliberately added,
in known concentrations, at specific
location in the microstructure
 Beneficial effect on properties or processing

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Point Defects (PD)

Vacancies and self-interstitials
 Produced when an atom or an ion is
missing from its normal site in the
crystal structure (Figure 1).
 Are introduced into metals & alloys
during solidification at high
temperatures.

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Point Defects (PD)

Point Defects:
(a)Vacancy
(b)Interstitial
(c)small substititional
atom
(d)large substititional
atom
(e)Frenkel defect
(f) Schottky defect

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Point Defects (PD)

Vacancies
Concentration of vacancies increases exponentially
with T:
Qv N A
N v  N exp( ) N 
kT A
 Nv = total no. of vacancies per cm3
 N = no. of atoms per cm3
 Qv = energy required for formation of a vacancy
 k = Gas constant = 1.38×10-23J/atom.°K
 k = Gas constant = 8.62×10-5 eV/atom.°K
 T = absolute temp in °K Mohammad Suliman Abuhaiba, Ph.D., PE
10 9/27/2015 9:43 PM
Point Defects (PD)

4.2 Vacancies and self-interstitials
 For most metals, the fraction Nv/N
just below the melting point is on
the order of 10-4
 A self-interstitial: an atom from the
crystal that is crowded into an
interstitial site, a small void space
that under ordinary circumstances is
not occupied
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Example 4.1
Calculate the equilibrium number of
vacancies per cubic meter for copper at
1000°C. The energy for vacancy formation
is 0.9 eV/atom; the atomic weight and
density (at 1000 °C) for copper are 63.5
g/mol and 8.4 g/cm3, respectively.

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Impurities in Solids
Addition of impurity atoms to a metal will
result in the formation of a solid solution
and/or a new 2nd phase depending on:
1. Kind of impurity
2. Concentrations
3. Temperature

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 Solvent: element or compound
present in greatest amount
 Solute: element or compound

present in a minor concentration

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Solid Solutions
A solid solution forms as:
1. Solute atoms are added to
host material
2. Crystal structure is maintained
3. No new structures are formed

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Solid Solutions
A solid solution is compositionally
homogenous
 impurity atoms are randomly &

uniformly dispersed within the
solid
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Substitutional Defects
 Introduced when one atom or ion is
replaced by a different type of atom
or ion
 Can be introduced either as an
impurity or as a deliberate addition.
 No. of defects is relatively
independent of T
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4.3 Impurities in Solids

 Examples:dopants such as P or B into Si.
 If we add Cu to Ni, Cu atoms will
occupy crystallographic sites where Ni
atoms would normally be present

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Rules for Substitutional solid solution:
1. Atomic size factor:
 difference in atomic radii between the two
atom types < 15%
 Otherwise, solute atoms will create substantial
lattice distortions and a new phase will form
2. Same Crystal structure for both
solvent and solute Mohammad Suliman Abuhaiba, Ph.D., PE
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Rules for Substitutional solid solution:
3. Electronegativity: comparable
electronegativity of the two atoms
4. Valences: a metal will have more of
a tendency to dissolve another
metal of higher valence than one of
a lower valence
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Interstitial Defects
 Formed when an extra atom or ion is
inserted into the crystal structure at a
normally unoccupied position.

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C atoms occupy interstitial sites in Fe

crystal structure, introducing a stress in the
localized region of the crystal in their
vicinity.

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 Ifthere are DLs in the crystals trying to

move around these types of defects,
they face a resistance to their motion,
making it difficult to create permanent
deformation in metals & alloys.
 This is one way of increasing strength of
metallic materials

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 No.
of interstitial atoms or ions in structure
remain nearly constant with T

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Specification of composition
Weight % basis
Atom % basis

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Composition Conversions

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Concentration in terms of mass of one
component per unit volume of material

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Average density & average atomic weight

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Example 4.2
Derive Equation 4.6a.

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Example 4.3
Determine the composition, in atom
percent, of an alloy that consists of 97 wt%
aluminum and 3 wt% copper.

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Dislocations - Linear Defects

 DLs are line imperfections in an
otherwise perfect crystal.
 3 types of DLs:
1. Screw
2. Edge
3. Mixed
 DLsare useful in increasing strength
of metals & alloys.
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Edge DL (EDL)
 Slicing partway through a perfect crystal,
spreading the crystal apart, & partly filling the cut
with an extra plane of atoms.
 Bottom edge of this inserted plane represents the
EDL.
 BV is perpendicular to the EDL

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Screw DLs (SDL)
 Cutpartway through a perfect crystal and then
skew the crystal one atom spacing.

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Screw DLs (SDL)
Following a crystallographic plane one rev
around axis on which crystal was skewed,
 start at a point x
 travel equal atom spacing in each
direction
 we finish one atom spacing below our
starting point (y)

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Screw DLs (SDL)
 The vector required to complete the loop
& return us to our starting point is the
Burgers vector (BV) b.
 The axis, around which we trace this path,
is the screw DL.
 BV is parallel to the SDL.

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Mixed DLs

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 When a shear force acting in direction of
BV is applied to a crystal containing a DL,
DL can move by breaking bonds between
atoms in one plane.
 The cut plane is shifted slightly to establish
bonds with the original partial plane of
atoms.
 This shift causes DL to move one atom
spacing to the side.
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 Ifthis process continues, DL moves through crystal
until a step is produced on the exterior of crystal;
the crystal has then been deformed.
 Speed with which DLs move in materials is close
to or greater than speed of sound.

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Figure 4.6: A
transmission electron
micrograph of a
titanium alloy in
which the dark lines
are dislocations.
51,450
(Courtesy of M. R. Plichta, Michigan
Technological University.)

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Interfacial Defects
External Surfaces
Along the external surface,
 crystal structure terminates
 Surface atoms are not bonded to
maximum number of nearest neighbors,
and are therefore in a higher energy state
than atoms at interior positions.
 bonds of these surface atoms that are not
satisfied give rise to a surface energy
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Interfacial Defects
External Surfaces
Along the external surface,
 To reduce this energy, materials tend
to minimize total surface area.
 For example, liquids assume a shape
having a minimum area - droplets
become spherical.

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Interfacial Defects
Surface defects (SD)
 SDs are the boundaries, or planes, that

separate a material into regions, each
region having the same crystal structure
but different orientations.

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Interfacial Defects
 Grains and grain boundaries.

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Interfacial Defects
By reducing the grain size,
 we increase no. of grains, and hence
increase amount of grain boundary
area.
 Any DL moves only a short distance
before encountering a GB and being
stopped, and strength of metallic
material is increased.
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Interfacial Defects
Phase Boundaries
 Phase boundaries exist in multiphase
materials, wherein a different phase exists
on each side of the boundary.
 Each of the constituent phases has its own
distinctive physical and/or chemical
characteristics.

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Interfacial Defects
Stacking Faults
 Occur in FCC metals
 Represent an error in stacking sequence
of CPP.
 Normally a stacking sequence of
ABCABCABC is produced in a perfect
FCC crystal

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Interfacial Defects
Stacking Faults
 Suppose the following sequence is
produced:
 ABC ABABC ABC
 This small region, which has HCP
stacking sequence instead of FCC
stacking sequence, represents a
stacking fault.
 Stacking faults interfere with the slip
process. Mohammad Suliman Abuhaiba, Ph.D., PE
47 9/27/2015 9:43 PM
Bulk or Volume Defects

 Includes:
 Pores
 Cracks
 Foreign inclusions
 Other phases
 Normally introduced during
processing and fabrication steps
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Atomic Vibrations
 Every atom in a solid material is vibrating
very rapidly about its lattice position
within the crystal.
 These atomic vibrations may be thought
of as imperfections or defects.
 At any instant of time not all atoms
vibrate at the same frequency and
amplitude, nor with the same energy.
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Atomic Vibrations
 At a given temperature there will exist a
distribution of energies for the
constituent atoms about an average
energy.
 Over time the vibrational energy of any
specific atom will also vary in a random
manner.

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Atomic Vibrations
 With rising temperature, this average
energy increases
 Temperature of a solid is a measure of
average vibrational activity of atoms
and molecules.
 At RT, a typical vibrational frequency is
on the order of 1013 vibrations / sec,
whereas the amplitude is a few
thousandths of a nanometer.
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Atomic Vibrations
 Many properties and processes in solids
are manifestations of this vibrational
atomic motion.
 For example, melting occurs when the
vibrations are vigorous enough to
rupture large numbers of atomic bonds.

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Microscopic Techniques
Microscopic Examination
 Grain size and shape are only two

features of what is termed microstructure.

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Microscopic Examination
 Applications of microstructural
examination:
1. Understand relation between properties &
structure
2. Predict properties of materials once these
relationships have been established.
3. Design alloys with new property combinations
4. Monitor and control results of heat treatment
5. Study the mode of mechanical fracture
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4.10 Microscopic Techniques

1. Optical microscopy
2. Electron microscope
 Transmission Electron microscope
 Scanning Electron microscope
3. Scanning probe microscopy

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Optical microscopy
 Used in a reflecting mode

 Contrasts in the image produced result
from differences in reflectivity of the
various regions of the microstructure
 Specimen surface must be ground and
polished to a smooth and mirror like finish

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Optical microscopy
 Microstructure is revealed using chemical
etching
 Chemical reactivity of grains of some
single phase materials depends on
crystalo-graphic orientation

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Optical microscopy
 In a polycrystalline
specimen, etching char vary
from grain to grain
 Small grooves form along
grain boundaries as a result
of etching.
 Atoms along GB regions are
more chemically active,
they dissolve at a greater
rate than those within the
grains. Mohammad Suliman Abuhaiba, Ph.D., PE
58 9/27/2015 9:43 PM
Optical microscopy
 GBs reflect light at an angle different from

that of grains themselves (F4-14)
 2000X

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Optical microscopy

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Electron Microscopy
 An image is formed using beams of
electrons
 A high velocity electron will become
wave like with a wave length that is
inversely proportional to its velocity
 The electron beam is focused and the
image formed with magnetic lenses
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Transmission Electron microscope (TEM)
 Image seen with TEM is formed by an
electron beam that passes through
specimen
 Transmitted beam is projected onto a
fluorescent screen or a photographic
film
 1000,000X

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Scanning Electron microscope (SEM)
 Surface of specimen to be examined is
scanned with a beam of electrons and
the reflected beam of electrons is
collected then displayed at the same
scanning rate on a cathode ray tube.
 The surface may or may not be polished
and etched but it must be electrically
conductive
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Scanning Electron microscope (SEM)
 Very thin metallic surface coating must

be applied to non-conductive materials
 Up to 50,000X

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Scanning Probe Microscopy (SPM)
 Neither light nor electrons is used to
form image
 Microscope generate a topographical
map on an atomic scale
 109X
 3-D magnified images
 Variety of environments

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SPM employ a tiny probe with a
very sharp tip that it brought into
close proximity of specimen
surface
Probe is raster scanned across the
plane of the surface
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During scanning, probe
experiences deflections
perpendicular to this plane in
response to electronic or other
interactions between the probe
and the specimen surface

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The in surface plane and out of
plane motions of the probe are
controlled by piezoelectric
ceramic components.

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Grain Size Determination

ASTM method
 Standard comparison charts
 Each is assigned a number ranging from
1 to 10 (grain size number) at 100X
n =2G-1
G =grain size number
 n = average number of grains per
square inch at 100X

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Grain Size Determination

ASTM method
number of grains per square inch at
magnification M, nM

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Example Problem 4.4

a. Determine the ASTM grain size number
of a metal specimen if 45 grains per
square inch are measured at a
magnification of 100.
b. For this same specimen, how many
grains per square inch will there be at a
magnification of 85?

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Example Problem 4.5

The following is a
schematic
micrograph that
represents the
microstructure of
some hypothetical
metal. Determine the
ASTM grain-size
number, G.

Ch4 Imperfections in Solids 2015

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9/27/2015

Home Work Assignment

Mohammad Suliman Abuhaiba, Ph.D., PE

Why Study Imperfections in Solids?

Point Defects (PD)

Point Defects (PD)

Mohammad Suliman Abuhaiba, Ph.D., PE

Point Defects (PD)

Mohammad Suliman Abuhaiba, Ph.D., PE

Point Defects (PD)

Mohammad Suliman Abuhaiba, Ph.D., PE

Point Defects (PD)

Point Defects (PD)

Mohammad Suliman Abuhaiba, Ph.D., PE

Mohammad Suliman Abuhaiba, Ph.D., PE

 Solute: element or compound

Mohammad Suliman Abuhaiba, Ph.D., PE

Mohammad Suliman Abuhaiba, Ph.D., PE

 impurity atoms are randomly &

4.3 Impurities in Solids

Mohammad Suliman Abuhaiba, Ph.D., PE

Mohammad Suliman Abuhaiba, Ph.D., PE

C atoms occupy interstitial sites in Fe

Mohammad Suliman Abuhaiba, Ph.D., PE

 Ifthere are DLs in the crystals trying to

Mohammad Suliman Abuhaiba, Ph.D., PE

Mohammad Suliman Abuhaiba, Ph.D., PE

Mohammad Suliman Abuhaiba, Ph.D., PE

Mohammad Suliman Abuhaiba, Ph.D., PE

Mohammad Suliman Abuhaiba, Ph.D., PE

Mohammad Suliman Abuhaiba, Ph.D., PE

Mohammad Suliman Abuhaiba, Ph.D., PE

Mohammad Suliman Abuhaiba, Ph.D., PE

Dislocations - Linear Defects

Dislocations - Linear Defects

Mohammad Suliman Abuhaiba, Ph.D., PE

Dislocations - Linear Defects

Mohammad Suliman Abuhaiba, Ph.D., PE

Dislocations - Linear Defects

Mohammad Suliman Abuhaiba, Ph.D., PE

Dislocations - Linear Defects

Mohammad Suliman Abuhaiba, Ph.D., PE

Dislocations - Linear Defects

Mohammad Suliman Abuhaiba, Ph.D., PE

Dislocations - Linear Defects

Dislocations - Linear Defects

Mohammad Suliman Abuhaiba, Ph.D., PE

Dislocations - Linear Defects

Mohammad Suliman Abuhaiba, Ph.D., PE

Mohammad Suliman Abuhaiba, Ph.D., PE

 SDs are the boundaries, or planes, that

Mohammad Suliman Abuhaiba, Ph.D., PE

Mohammad Suliman Abuhaiba, Ph.D., PE

Mohammad Suliman Abuhaiba, Ph.D., PE

Mohammad Suliman Abuhaiba, Ph.D., PE

Bulk or Volume Defects

Mohammad Suliman Abuhaiba, Ph.D., PE

Mohammad Suliman Abuhaiba, Ph.D., PE

 Grain size and shape are only two

Mohammad Suliman Abuhaiba, Ph.D., PE

4.10 Microscopic Techniques

3. Scanning probe microscopy

Mohammad Suliman Abuhaiba, Ph.D., PE