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MAPPH5XX MATERIAL
SCIENCE

Brighton. S. Mpofu

I know that I know nothing

- Socrates
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Cubic Crystal Structures

• Atoms per unit cell

• Coordination number

• Atomic packing factor

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• Lattice parameter – atomic structure relationships

• Examples

• Stacking sequence

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Atomic Radius – Lattice Parameter Relationships &

Packing Factor: Atomic Hard-Sphere Model
𝑵𝒇 𝑵 𝒄
𝑵 = 𝑵𝒊 + +
𝟐 𝟖

Reduced-Sphere
Unit Cell

Hard-Sphere
Unit Cell

𝑽𝒂𝒕𝒐𝒎𝒔 𝒊𝒏 𝒖𝒏𝒊𝒕 𝒄𝒆𝒍𝒍

𝑨𝑷𝑭 =
𝑽𝒖𝒏𝒊𝒕 𝒄𝒆𝒍𝒍 4𝑟 4𝑟
𝑎0 = 2𝑟 𝑎0 = 𝑎0 =
𝒏𝑨
3 2
𝝆=
𝑽𝒄 𝑵𝑨 APF= 0.52 APF= 0.68 APF= 0.74
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Simple Cubic (SC) Structure

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Simple Cubic:
Lattice Parameter – Atomic Radius Relationship

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Simple Cubic: Atomic Packing Factor

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Body Centered Cubic (BCC):

Lattice Parameter – Atomic Radius Relationship

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Body Centered Cubic: Atomic Packing Factor

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Face Centered Cubic (FCC):

Lattice Parameter – Atomic Radius Relationship

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Face Centered Cubic: Atomic Packing Factor

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Close-Packed Directions & Planes

The packing of atoms into a minimum total volume is close packing
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Stacking Sequence of Close-Packed Planes

𝐴𝐵𝐴𝐵𝐴𝐵 in HCP Structure 𝐴𝐵𝐶𝐴𝐵𝐶𝐴𝐵𝐶 in FCC/CCP Structure

Unit Cell
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Slip Direction on Close-Packed Plane

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Interstitial Sites
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Interstitial Sites: BCC Unit Cell

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Microstructure-Property Relationships
Microstructure-sensitive Properties Microstructure-insensitive Properties

• Strength • Density
• Toughness • Melting point
• Elongation • Modulus
• Thermal conductivity • Specific heat
• Electrical conductivity • Expansion coefficient
• Coercive field • Heat of fusion
• Energy product • Heat of vaporization
• Saturation magnetization
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Imperfections in the atomic and ionic arrangement

3.4 – 3.5
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Defects in Crystal
Useful Undesired
1. P-type & n-type doping in
semiconductors • Dislocations in computer
2. Strengthening metals & alloys
chips
o Strain hardening: dislocation density
control
o Solid-solution strengthening: • Impurities in Cu conductor
introduction of substitutional or interstitial
atoms for microelectronics
o Grain-size strengthening: increasing #
of grains or reducing size of grains
o Precipitation strengthening
o Second-phase strengthening

3. Novel properties e.g. red ruby

(Chromium oxide in Alumina)

4. Precipitates in flux-pinning in
superconductors
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Types of Defects
• Point defects

• Line defects/dislocations

• Surface/planar defects

• Volume defects
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Point Defects: Intrinsic

Intrinsic defects appear in a pure material

Vacancy Interstitial Atom

• Vacancies are present in a significant Because the interstitial sites in most

concentration in all crystalline materials crystalline solids are small (or have an
• The rate of diffusion on the crystal unfavorable bonding configuration, as,
lattice is largely governed by the e.g., in the diamond lattice) interstitials are
concentration of vacancies
high-energy defects that are relatively
• Vacancies & interstitials can be
produced in materials by plastic uncommon.
deformation & high-energy particle
irradiation
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Visualization of Vacancy: SPM

Scanning Probe Microscopy (SPM) e.g. Scanning Tunneling
Microscopy (STM) can be utilized to visualize atomic size defects

Scanning probe micrograph showing a vacancy

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Point Defects in Ionic Crystals: Intrinsic

Frenkel Defects Schottky Defects

An atom is displaced from its In ionic crystals, a pair of vacancies

regular lattice site to an interstitial i.e. anion vacancy and cation
site creating a pair of a vacancy vacancy is called a Schottky defect.
and interstitial site. The defect pair In ionic crystals a single vacancy
is referred to as a Frenkel defect. cannot occur by itself because of
the constraint of charge neutrality
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Difference Between Schottky and Frenkel Defects

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Point Defects: Extrinsic

Small Substitutional Atom Large Substitutional Atom

• The extrinsic point defects are foreign atoms, which are called solutes if they
are intentionally added to the material and are called impurities if they are not
• The foreign atom may occupy a lattice site, in which case it is called a
substitutional solute (or impurity) or it may fill an interstitial site, in which case it
is called an interstitial solute
• Small atoms, e.g. H, C and N are often found in interstitial sites. Larger atoms
are usually substitutional.
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Interstitial Sites: Tetrahedral & Octahedral

For both FCC & BCC there are two types of interstitial sites i.e. tetrahedral & octahedral

FCC BCC

Octahedral sites have a

Tetrahedral sites have a
coordination number of 6
coordination number of 4
C forms an interstitial solid solution when added to Fe & maximum C concentration ~2%
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Summary: Point Defects

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Assignment

The Kröger-Vink Notation

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Some of the atoms are misaligned

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• Occur by atomic planes sliding over each other

• Dislocations are linear defects: they are lines through

the crystal along which crystallographic registry is lost
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Edge Dislocation
• The edge defect can be easily visualized as an extra half-
plane of atoms in a lattice
• The dislocation in the top half of the crystal is slipping one
plane at a time as it moves to the right from its position in
image (a) to its position in image (b) and finally image (c). In
the process of slipping one plane at a time the dislocation
propagates across the crystal. The movement of the
dislocation across the plane eventually causes the top half
of the crystal to move with respect to the bottom half.

(a) (b) (C)

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Screw Dislocations

The motion of a screw dislocation is also a result of

shear stress, but the defect line movement is
perpendicular to direction of the stress and the atom
displacement, rather than parallel

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Dislocation
Comparison: Edge & Screw Burgers Vector b
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Dislocations TEM Imaging

• Dark lines are dislocations

in TEM micrograph

• Dark Field (DF) or Bright

Field TEM imaging is
mostly used to visualize
dislocations
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Motion of an Edge Dislocation due to a

Shear Stress

• Dislocation motion along a crystallographic direction is called slip

• There must be a local shear stress in an appropriate direction on the dislocation
for slip to occur
• Dislocation slip allows plastic deformation to occur at a much lower stress than
would be required to move a whole plane of atoms past another

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Factors Affecting Slip in Metallic Structures

Structure-property relationships:
• Close-packed planes vs ductility
• # of slip systems vs ductility
• Cross-slip vs ductility
• Crystallinity vs ductility
𝑐
• ratio vs brittleness
𝑎
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Slip in Metallic Structure

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Stacking Sequence Disruption

A disruption of the long-range stacking sequence can

produce two common types of crystal defects:
i. A stacking fault &
ii. A twin

 A change in the stacking sequence over a few atomic spacings

produces a stacking fault
 Stacking faults occur in FCC structure

 A change over several atomic spacing distance produces a twin

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Stacking Faults
A stacking fault is a one or two layer interruption in the stacking sequence of atom planes
Intrinsic Stacking Fault Extrinsic Stacking Fault

- Removal of layer (plane) - Introduction of an extra layer

- Sequence before & after not disrupted - Sequence before & after disrupted
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Visualization of Stacking Sequence: HRTEM

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Stacking Faults Visualization: BF/DF & ED

Dark Field Image Electron Diffraction: Streaking

5 1/nm
50 nm

Boron carbide nanowire

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Twin Boundaries
• Deformation twinning is
a process in which a
region of a crystal
undergoes a
homogeneous shear
that produces the
original crystal structure
in a new orientation

• The twin boundaries

interfere with the slip
process & increase the
strength of the metal
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Twinning
Normal FCC Lattice Twin Fault
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Twinning: Electron Diffraction

5 1/nm

Diffraction spots split into two

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Twinning: TEM Imaging

HRTEM Image Dark Field Image

50 nm

A special mirror image misorientation of Bright field image will give the opposite
the crystal structure contrast (bright will be dark & vice versa)
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Summary: Stacking Faults & Twinning

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Stacking Faults or Twin: Diffraction Pattern

Stacking Faults: Streaking Twin: Splitting of Spots
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Grain Boundaries
• Polycrystalline solids
consist of a large number
of randomly oriented
grains separated by grain
boundaries
• Each grain is a single
crystal & may contain point
defects
• Grain size can be controlled thru • A notable feature of the
solidification, alloying or heat boundary structure is that
treatment the region of disorder is
• Grain size vs yield strength of a metal very narrow, being limited
(structure-property relationship!)
𝐾
to one or two ‘atoms’ on
Hall-Petch equation: 𝜎𝑦 = 𝜎0 + each side of the boundary
𝑑
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Grain Size Controlling Metal Properties:

Hall-Petch Equation
• The properties of a material can be controlled by controlling the
grain size
• Increasing the number of grains increases the amount of grain
boundary area
• Any dislocation moves only a short distance before
encountering a grain boundary (therefore the strength of the
metallic material is increased)
• The Hall-Petch equation relates the grain size to the yield
strength:
𝜎𝑦 = 𝜎0 + 𝐾𝑑 −1 2
• 𝜎𝑦 =the yield strength
• 𝑑 =average diameter of the grains
• 𝜎0 & 𝐾 are constants for the metal
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Phase Boundaries
A phase boundary between FCC
A Phase Boundary Separating silicon (Si) and hexagonal
FCC and BCC iron palladium silicide (Pd2Si)

HRTEM Images https://www.tf.uni-kiel.de/matwis/amat/iss/kap_5/backbone/r5_3_2.html#_112

T. Moritani, N. Miyajima, T. Furuhara, T. Maki: "Comparison of interphase boundary FÖLL, H., HO, P., TU, K.N.: "Cross-sectional TEM of silicon-silicide interfaces" J. Appl. Phys.
structure between bainite and martensite in steel" Scripta Materialia 47 (2002) p. 193–199 52 (1981) o. 25
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Phase Boundaries
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Antiphase Boundaries
"Anti-phase boundary" separates two adjacent crystals which have the same
crystallographic orientation but have a 180°phase shift (a shift of half period) each
other. Anti-phase boundaries frequently appear in the ordered phase of a binary alloy

High resolution STEM HAADF showing strontium titanate, SrTiO3, (a) an anti-
phase boundary and (b) an intensity profile along a line drawn across the APB in (a).

Tse, Y.Y., McMitchell, S.R.C., Jackson, T.J., Jones, I.P. and Genc, A., 2012. Line defects, planar defects and voids in SrTiO3 films grown on MgO by pulsed laser and pulsed laser interval
deposition. Thin Solid Films, 520(9), pp.3440-3447.
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Antiphase Boundaries
An antiphase domain (APD) is a type of crystallographic defect in which the
atoms in a region of a crystal are configured in the opposite order to those in the
perfect lattice system

DOI: 10.1016/j.actamat.2016.09.035
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Volume Defects
• Defects such as precipitates, voids and bubbles,
pores, cracks, foreign inclusion have important
effects on properties of solids e.g. interaction of
dislocation and precipitates play a vital role in
development of high – strength steel

• Voids are small regions were there are no atoms i.e.

clusters of vacancies

• Precipitates: are formed by clustering of impurity

atoms in a crystal.
• There is usually a maximum concentration to Precipitates
which the atoms of element B can be dissolved in
solution in a crystal of element A. Above this
solubility limit, the excess B atoms tend to
precipitate (as B or compound of A and B)
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Summary on Common Defects in Crystals

Type of Imperfection Description
Point defects
Interstitial Extra atom in an interstitial site
Schottky defect Atom missing from correct site
Frenkel defect Atom displaced to interstitial site creating nearby vacancy

Line defects
Edge dislocations Row of atoms marking edge of a crystallographic plane extending only
part way in crystal
Screw dislocations Row of atoms about which a normal crystallographic plane appears to
be spiral
Plane defects
Lineage boundary Boundary between two adjacent perfect regions in the same crystal
that are slightly tilted with respect to each other

Grain boundary Boundary between two crystals in a polycrystalline solid

Stacking fault Boundary between two parts of a closest packing having alternate
stacking sequences
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