MSE 154 Principles of Materials Science

Department of Materials Engineering

2
Forms of Assessment

Attendance 5

Assignments 5

Quizzes 5

Mid-Sem Exam 15

Final Exam 70

Total 100
 Course outline
Introduction
 Atomic Structure: Primary Inter-atomic bonds, Secondary bonds
 Fundamentals of crystal structures: Unit cells, Theoretical
Computations( Unit cell volume, density, etc)
 Polymorphism and allotropy
 Metallic and ceramic crystal structures
 Crystal systems
 Crystallographic direction and planes
 Miller indices
 Linear and planar atomic densities
 Determination of crystal structures: X-ray diffraction and Bragg’s law
4
 Introduction
What type of materials have been used for these beverage containers?

A
C

B
5
 History of Materials Science and Engineering
Mankind has been designated with the dominated material at a particular time

Bronze age
Stone age Iron age

Modern age Steel age

6
 Introduction Cont…..
• Materials Science: Studying the relationship between the structures and properties of
materials.

• Structures: Arrangement of internal components (subatomic, atomic, microscopic and

macroscopic)

• Properties: Trait in terms of kind and magnitude of response to imposed stimuli.

• Properties of a material depends on its composition and microstructure
• Properties such as: Mechanical, thermal, electrical, magnetic, optical, quantum
mechanical and deteriorative

• Materials Engineering: The discipline of designing or engineering the structure of a

material to produce a predetermined set of properties based on established structure-
property correlation
7
 Introduction Cont….
What is Materials Science and Engineering?
• Relationship between the four components:

Processing/synthesis

Structure Properties

Performance

8
 Introduction Cont…..
Why Study Materials Science and Engineering?
Materials science and engineering plays a vital role in this modern age of
science and technology.

Example for material selection purposes

• In-service properties
• Deterioration of parts in service
• Economics aspect: Cost of finished product

9
 Introduction Cont….
 Types of Materials

 Advanced Materials: such as Semiconductors, biomaterials, energy materials,

nanomaterials, smart materials, etc. are obtained from these four main class of
materials
10
 Types of materials
Metals
Constitute one or more metallic elements
 Example:- Iron, Copper, Aluminum, Lead, Zinc, etc.
 Metallic element may combine with nonmetallic elements.
 Example:- Silicon Carbide, Iron Oxide,
Orderly atomic arrangement
 Inorganic and have crystalline structure.
Relatively dense
 Good thermal and electric conductors
Metals and Alloys

Ferrous Nonferrous
Eg: Steel, Eg:Copper
Cast Iron Aluminum

11
 Introduction Cont….
Metals
• Chemical make up of metallic elements
• Accounts for most of its properties

• Some Characteristics
• Relatively good ductility
• Stiffness
• High strength
• Formability, opaque

• Main uses:
• Structural and
• Load bearing applications

12
 Introduction Cont….
• Some metallic products

13
 Types of Materials
Ceramic Materials
 Compounds between metallic and nonmetallic elements that are
chemically bonded together.
 Nonmetallic elements (Carbides, nitrides, sulfides, oxides)
 Inorganic but can be either crystalline, noncrystalline or mixture of
both.
 High hardness, strength and wear resistance.
 Very good insulator. Hence used for furnace lining for heat treating
and melting metals.
 Also used in space shuttle to insulate it during exit and reentry into
atmosphere.
 Can withstand harsh environments and high temperature regions
 Other applications : Abrasives, construction materials, utensils etc.

 Example:- Porcelain, Glass, Silicon nitride.

14
 Introduction Cont….
• Ceramic Materials
Optical properties Polycrystal with low
porosity
 Aluminum oxide can be
 Transparent
 Translucent
 Opaque

Single Crystals Polycrystal with

high porosity

Adapted from Fig. 1.2 Callister 9e, (Specimen preparation,

P.A. Lessing; photo by J. Telford)
15
 Introduction Cont….
• Some ceramic products

16
 Introduction Cont….
• Polymers

• Include rubbers, plastics and many adhesives

• Most of them are organic compounds based on C, H

and other non metallic elements(N, Cl, Si, O etc)

• Large molecular structures, often chain-like in nature

that have a backbone of C - atoms

• Examples PE, PS, PC, PVC, PP, nylon, silicone rubber etc
17
 Introduction Cont….
• Polymeric Materials

Characteristics
 Mostly noncrystalline.
 Some are mixtures of crystalline and noncrystalline regions.
 Poor conductors of electricity and hence used as insulators.
 Low strength, high ductility.
 Low densities and decomposition temperatures.
 Relatively inert chemically and un-reactive in many environments
 Can be formed into complex shapes

 Examples :- Poly vinyl Chloride (PVC), Polyester, Polyethylene, Elastomers etc

 Applications :- Appliances, DVDs, Fabrics etc.

18
 Introduction Cont….
• Some Polymeric products

19
 Introduction Cont….
Composite Materials
 Made by combining two or more materials – often ones that have very different
properties
 The two materials work together to give the composite unique properties

 Examples:
• Natural: Wood (Cellulose and lignin), bone (hydroxyapatite and collagen)
• Synthetic:
• Concrete
• Fiberglass; GFRP ( Glass fibers embedded in polymer, e.g. epoxy)
Properties: Strong, stiff-fibers, flexible and light-polymer
• Carbon fiber-reinforced polymer (CFRP) composite
CFRP has very peculiar application but very
expensive
• Aircraft and Aerospace, golf clubs, tennis rackets etc

20
Introduction Cont….

Room Temperature Density, Callister 9e

21
Introduction Cont….

Room Temperature Stiffness, Callister 9e

22
Introduction Cont….

Room Temperature Strength, Callister 9e

23
Introduction Cont….

Room Temperature Electrical conductivity, Callister 9e

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 Lecture 2
From the Student’s guide 2013 version page 58 4d

“A student shall attend all lectures, seminars, workshop sessions and

practical prescribed for the courses for which he/she registered as a
pre-condition for writing an examination.”
 Introduction Cont….
Semiconductors

• Electrical properties intermediate between

• Electrical conductors: metals & metal alloys
• and insulators: polymers & ceramics

Examples
• Group IV semiconductor(Ge, Si, C-diamond)
• Group III-V compounds(GaS, InSb, GaP, InAs)

27
 Introduction Cont….
Semiconductors

 Electrical x’tics extremely sensitive to minute impurity atom concentrations

 Applications:
• In electronic devices such as diodes, transistors etc,
• Communication applications and
• Computer industry over the last 3 decades

28
 Introduction Cont….
Biomaterials

• Components implanted into the body to replace a diseased or

damaged part

• They must not produce toxic substances

• They must be compatible with the body tissues

• What class materials do you think can be used as biomaterials?

29
 Introduction Cont….
Smart Materials
• Are materials that have one or more properties that can
be significantly altered in a controlled fashion by external
stimuli, such as stress, temperature, moisture, pH,
electric or magnetic fields
• Examples
• Piezoelectric materials
• Shape memory alloys
• Magnetic shape memory alloys
• PH sensitive polymers

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 Review of Atomic Structure
The bonding mechanisms between atoms are closely related
to the structure of the atoms themselves.

Atom = Nucleus (protons + neutrons) + electrons

Charges:
Electrons and protons have negative and positive charges of the same
magnitude, 1.6 × 10-19 Coulombs.
Neutrons are electrically neutral.
Masses:
Protons and Neutrons have the same mass, 1.67 × 10-27 kg.
Mass of an electron is much smaller, 9.11 × 10-31 kg and
can be neglected in calculation of atomic mass.
31
 Review of Atomic Structure

The atomic mass (A) = mass of protons + mass of neutrons

# protons gives chemical identification of the

element
# protons = atomic number (Z)
# neutrons defines isotope number

32
 Review of Atomic Structure
The atomic mass unit (amu) is often used to express atomic
weight. 1 amu is defined as 1/12 of the atomic mass of the
most common isotope of carbon atom that has 6 protons
(Z=6) and six neutrons (N=6).
Mproton ≈ Mneutron = 1.66 x 10-24 g = 1 amu.
The atomic mass of the 12C atom is 12 amu.

The atomic weight of an element = weighted average of the atomic

masses of the atoms naturally occurring isotopes.
Atomic weight of carbon is 12.011 amu.
The atomic weight is often specified in mass per mole.

33
 Review of Atomic Structure
A mole is the amount of matter that has a mass in grams equal to
the atomic mass in amu of the atoms (A mole of carbon has a
mass of 12 grams).

The number of atoms in a mole is called the Avogadro

number, Nav = 6.023 × 1023 mol-1

1 amu/atom = 1 gram/mol

Example:
Atomic weight of iron = 55.85 amu/atom = 55.85 g/mol

34
 Review of Atomic Structure
• Some simple calculations
The number of atoms per cm3, n, for material of density d
(g/cm3) and atomic mass M (g/mol):
n = Nav × d / M
Graphite (carbon): d = 2.3 g/cm3, M = 12 g/mol
n = 6×1023 atoms/mol × 2.3 g/cm3 / 12 g/mol
= 11.5 × 1022 atoms/cm3
Diamond (carbon): d = 3.5 g/cm3, M = 12 g/mol
n = 6×1023 atoms/mol × 3.5 g/cm3 / 12 g/mol
= 17.5 × 1022 atoms/cm3
Water (H2O) d = 1 g/cm3, M = 18 g/mol
n = 6×1023 molecules/mol × 1 g/cm3 / 18 g/mol
= 3.3 × 1022 molecules/cm3
35
 Atomic Bonding in Solids
Bonding forces and energies
• At large distances atomic interactions are negligible
• But what happens when 2 isolated atoms are brought
close to each other
– They exert forces on each other
– What effect do you think these forces will have on these 2 atoms?

• FN = FA + FR

36
Atomic bonding in solids

This is typical potential well for two interacting atoms

37
 Atomic Bonding in Solids
Bonding forces and energies
• FA is due to type of bond that exists
between atoms
• FR comes to play when outer electron
shells
overlap at close distance
• FA + FR = O (State of Equilibrium)
• Atom centres remain at equilibrium
distance ro ~
(0.3nm)
38
Atomic Bonding in Solids
(a) The dependence
of repulsive, attractive and net
forces on inter-atomic
separation for 2 isolated
atoms

(b) The dependence

of repulsive, attractive and net
Potential energies on
interatomic
separation for 2 isolated
atoms

39
 Atomic Bonding in Solids
• Bonding forces and energies
Mathematically, E= 𝐹𝑑𝑟
Force-potential energy relationship for two atoms
But for Atomic systems,
∞
EN= 𝑟 𝐹𝑁 𝑑 𝑟
∞ ∞
EN = 𝑟
𝐹𝐴𝑑 𝑟 + 𝑟 𝐹𝑅𝑑 𝑟
= EA + ER
• At ro, the 2 atoms counteract any attempt to separate them (by attractive
force) or push them together( by repulsive force)…Simply, they are bound
together

40
 Atomic Bonding in solids
Bonding forces and energies
• The net curve for the energy-distance curve has a
potential energy trough or well around its minimum

• What can u say about ro in (a) and Eo in (b)?

• Eo is called bonding energy i.e. energy required to

separate the 2 atoms to infinite distance

• In reality, complex situation arises since we have

interactions among large number of atoms
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 Atomic Bonding in solids
Bonding forces and energies
• Eo may be associated with each atom though
– the shape of the E - r curve as well as
– the magnitude of Eo differs from material to material
• Curve shape and magnitude of Eo depends on type of atomic bonding

• Most material properties depend on Eo as well as the

curve shape, and the bonding type

• Correlation between bonding energies and material properties???

42
 Classes of Materials (Advanced Materials)
Categories of Solids

 There are three categories of solids, based on their conducting

properties:

o Conductors

o Semiconductors

o Insulators

 Semiconductors are materials whose electrical properties lie between

Conductors and Insulators.

o E.g. : Silicon and Germanium

 Classes of Materials
Semiconductors

Electrical Resistivity
and Conductivity of
Selected Materials
at 293 K
 Classes of Materials
Semiconductors
 Examples
o Group IV semiconductor (Ge, Si, C-diamond)
o Group III-V compounds (GaS, InSb, GaP, InAs)

 Electrical characteristics extremely sensitive to minute impurity atom

concentrations
 Applications:
o In electronic devices such as diodes, transistors etc.
o Communication applications and
o Computer industry over the last 3 decades
 Classes of Materials
Biomaterials
 Any substance (other than drugs) or combination of substances synthetic or
natural in origin, which can be used for any period of time, as a whole or as a
part of a system which treats, augments, or replaces any tissue, organ, or
function of the body.
 Components implanted into the body to replace a diseased or damaged part.
 They must not produce toxic substances. They must be biocompatible.
 Biocompatibility is the ability of a material to perform with an appropriate
host response in a specific application.
 Which one class of material do you think can be used as a bone replacement?
 Metals, ceramics, polymers, composites and semiconductors may all be
used
 Classes of Materials
Discussion

1) What class (based on chemical make up) of

material will you advice for a coffee cup
and why?

2) What class of material will you choose for

the handle of an aluminum cooking ware to
be used on an electric cooker and why?

3) What class of material will you advice for a

Lower leg bone
broken tibia/fibula replacement and why?
 Assignment
Due: Latest 15th February, 2018 at 11:05 am.

 Research on the following. Handwritten per page per question is

required on a foolscap sheet.

1) SMART materials

2) Contact lenses and what kinds of materials they are made

from.
 Atomic Bonding in Solids
Bonding Forces and Energies
 Knowledge of the interatomic forces that bind atoms together in solids
helps us to understand their physical properties better
 Solids are very compact because atoms are strongly bonded together
 Let’s consider 2 isolated atoms.
o At large distances (atomic scale ~ nm) atomic interactions are negligible
o But, when brought close enough to each other, they exert forces on each other
o What effect will result between the 2 atoms due to these forces?

r
 Atomic Bonding in Solids
Bonding Forces and Energies

 FN = FA + FR

 FA, force of attraction between the atoms, is dependent on the type of

bond that exists between the 2 atoms

 FR, force of repulsion between the atoms, depends on closeness of the

outer electron shells

 FA + FR = O (State of equilibrium)

 Atom centres remain at equilibrium distance ro ~ (0.3 nm)

 Atomic Bonding in Solids
Bonding Forces and Energies
 Mathematically, the Force-potential energy relationship for two atoms
is 𝐸 = 𝐹𝑑𝑟
 But for atomic systems,
𝑟 𝑟
𝐸𝑁 = 𝐹 𝑑𝑟
∞ 𝑁
= (𝐹 𝑑𝑟
∞ 𝐴
+ 𝐹𝑅 𝑑𝑟)
𝐸𝑁 = 𝐸𝐴 + 𝐸𝑅
 At distance ro, the 2 atoms counteract any attempt to
o separate them (by attractive force) or
o push them together (by repulsive force)
 Simply, they are bound together, stable, comfortable, in equilibrium
 Atomic Bonding in Solids
Bonding Forces and Energies
 The net curve for (a) The dependence of
the P.E – r curve repulsive, attractive and net
has a trough or forces on inter-atomic
well around its separation for 2 isolated
atoms
minimum

 Eo is called
bonding energy (b) The dependence of
i.e. energy repulsive, attractive and
required to net Potential energies on
separate the 2 inter-atomic separation for
2 isolated atoms
atoms to infinite
distance
 Atomic Bonding in Solids
Bonding Forces and Energies
 Eo is the energy required to separate the 2 atoms to infinite distance
 Eo may be associated with each atom via
o the shape of the E – r curve as well as
o the magnitude of Eo
 NB: For every material, P.E – r curve shape and magnitude of Eo
depends on type of atomic bonding it has
 Most material properties depend on Eo as well as the curve shape, and
the bonding type
 What is the correlation between bonding energies and melting
temperature of solid materials???
 Atomic Bonding in Solids
Ionic Bonds

 Found in compounds made of metallic and non-metallic elements

 Metallic element donates electron to the non metallic element, why???

 Coulombic bonding forces, i.e. attraction between positive and

negative ions by virtue of their net electrical charge

 Non-directional

 For a stable system, positive ions must have negative nearest neighbors
and vice versa

 Ionic bonds are predominant in ceramic materials

 Atomic Bonding in Solids
Ionic Bonds

 For 2 ions, EA and ER are functions of inter-

atomic distance (r)
𝑨 𝑩
𝑬𝑨 = − and 𝑬𝑹 =
𝒓 𝒓𝒏

 A, B and n are constants whose values

depend on the particular ionic system

 n is approximately 8 for most ionic

systems
𝟏
𝑨= 𝒁𝟏 𝒆 𝒁𝟐 𝒆
𝟒𝝅𝝐𝒐
 Atomic Bonding in Solids
Ionic Bonds

 For NaCl, a typical e.g. of ionic bond, work done to remove electron
from Na atom is 5.14 eV i.e. creating a cation

 Transfer of electron to a vacant site in Cl atom, system gains 4.02 eV,

i.e. creating an anion

 Work done in creating isolated ions Na+ and Cl- is 1.12 eV, i.e. (5.14 eV
– 4.02 eV)

 This energy is recovered when ions are brought closer to ro???

 Atomic Bonding in Solids
Ionic Bonds

Formation of NaCl ionic bond Formation of ionic bond viewed in

between Na and Cl atoms terms of energy
 Atomic Bonding in Solids
Ionic Bonds

Bonding energies and melting temperatures for ionic materials

Melting
Substance Bonding energy
temperature
eV/atom, ion,
kJ/mol (oC)
molecule
NaCl 640 3.3 801
MgO 1000 5.2 2800
 Reading Assignment
 Atomic structure (Atomic number, isotope, atomic weight,
atomic mass unit

 Atomic models (Bohr’s atomic model, wave-mechanical model)

 Quantum numbers

 Electronic configurations (Electron state, Pauli’s exclusion

principle, ground state, electron configuration, valence electron)

 Periodic table: Electronegativity/elements

 Atomic Bonding in Solids
Covalent Bonds
 Stable configuration obtained by sharing of electrons between 2
adjacent atoms
 Atoms involved contribute at least an electron
 Bond is directional
 Found in
1) nonmetallic elemental molecules (Cl2, H2, F2 etc) - Non-solids
2) molecules of dissimilar elements (HNO3, HF, HCl etc) - Non-solids
3) elemental solids, e.g. diamond, silicon, germanium
4) solid compounds such as GaAs, InSb and SiC
 Atomic Bonding in Solids
Covalent Bonds
 Bonds are directional and forms specific angles
 In silicon, the arrangement produces a
tetrahedron and forms angle of 109.5o
 In reality, most inter-atomic bonds are partially
covalent and partially ionic
 For 2 elements A and B, the percent ionic
character (% IC ) of the bond between them (A
being most electronegative) is
% 𝐼𝐶 = 1 − 𝑒𝑥𝑝 − 0.25 𝑋𝐴 − 𝑋𝐵 2 × 100
 Atomic Bonding in Solids
Covalent Bonds
 The greater the difference in
electronegativities between the elements
the more ionic the bond and vice versa
 The sharing of electrons leads to reduction
in energy, therefore creating a stable bond
 For a covalent bond,
𝐴 𝐵
𝐸𝑜 = − 𝑚 + 𝑛 Energy versus interatomic
𝑟 𝑟
distance for covalent bonds
where m < n, 1st part is EA and 2nd is ER
 Why must the condition (m < n) must be
met for a covalent bond to form???
 Atomic Bonding in Solids
Covalent Bonds

Bonding energies and melting temperatures for covalent materials

Melting
Substance Bonding energy
temperature
eV/atom, ion,
kJ/mol (oC)
molecule
Si 450 4.7 1410
C (Diamond) 713 7.4 >3550
 Atomic Bonding in Solids
Ionic and Covalent Bonds
 Atomic Bonding in Solids
Metallic Bonds
 Dominant in metals and their alloys though they are not the only
bonds
 They are non-directional
 Highest energy electrons (which ones???) leave the atom to form a sea
of freely wandering electrons (Reason for easy electric and heat
conductivity)
 Positively charged ion cores created
 Net charge of ion cores is equal in magnitude to the total valence
electron charge per atom
 Electrons prevent ion cores from repelling each other and serve as a
“glue” for bonding
 Atomic Bonding in Solids
Metallic Bonds
 Metallic bonding is found for group 1A and IIA
elements and all elemental metals
 Bonding energies and melting temperatures for
some metallic materials
Melting
Bonding energy
temperature
Substance
eV/atom, ion,
kJ/mol (oC)
molecule
Hg 68 0.7 -39
Al 324 3.4 660
Fe 406 4.2 1538
W 849 8.8 3410
 Atomic Bonding in Solids
Metallic Bonds
 Atomic Bonding in Solids
Secondary Bonds/Van der Waal Forces
 Weaker relative to primary bonds
 Bonding energy ~ 10kJ/mol (0.1eV/atom)
 Its presence is mostly over shadowed by the primary bonds
 Bonding forces arise from atomic and molecular dipoles

 Electric dipole arise when there is separation of negative and positive

portions of an atom or molecule and therefore bonding is coulombic
 Atomic Bonding in Solids
Secondary Bonds/Van der Waal Forces
1) Fluctuating induced dipole bonds
2) Polar molecule – induced dipole bonds
3) Permanent dipole bonds

Fluctuating induced dipole bonds

 Atom or molecule is electrically symmetric
 Vibrational motion can cause instantaneous distortion
 This leads to the creation of small electric dipoles
 Dipoles induce adjacent atoms or molecules to also become dipoles
 Atomic Bonding in Solids
Secondary Bonds/Van der Waal Forces
Fluctuating induced dipole bonds
 These forces are temporal

Schematic representation of (a) Electrically symmetric atom and (b) an induced atomic dipole
 Atomic Bonding in Solids
Secondary Bonds/Van der Waal Forces

Polar Molecule – induced dipole bonds

 Electrically asymmetric arrangement of

positive and negative charged regions of
molecule creates permanent dipoles

o E.g. HCl molecule

Schematic representation of
hydrogen chloride (HCl) molecule
 Polar molecules can induce dipoles in
adjacent non-polar molecule and make
it polar leading to attraction
 Atomic Bonding in Solids
Secondary Bonds/Van der Waal Forces

Permanent dipole bonds

 Exist between 2 adjacent polar

molecules

 Typical example is hydrogen

bonding???

o e.g. a covalent bond between Hydrogen bonding in hydrogen fluoride

hydrogen and fluorine
 Atomic Bonding in Solids
Secondary Bonds/Van der Waal Forces

Fluctuating Polar molecule -

Permanent dipole
Induced dipole Induced dipole

What is the order of bond strength???

 Atomic Bonding in Solids

Bonding energies and melting temperatures for various materials

Melting
Bonding energy
Bonding temperature
Substance
Type eV/atom, ion,
kJ/mol (oC)
molecule
Van der Ar 7.7 0.08 -189
Waals Cl2 31 0.32 -101
NH3 35 0.36 -78
Hydrogen
H2O 51 0.52 0
 Atomic Bonding in Solids
Bonding Energies (Summary)
Melting
Bonding energy
Type of temperature
Substance
Bonding eV/atom, ion,
kJ/mol (oC)
molecule
NaCl 640 3.3 801
Ionic
MgO 1000 5.2 2800
Si 450 4.7 1410
Covalent
C (Diamond) 713 7.4 >3550
Al 324 3.4 660
Metallic Fe 406 4.2 1538
W 849 8.8 3410
Ar 7.7 0.08 -189
Van der Waals
Cl2 31 0.32 -101
NH3 35 0.36 -78
Hydrogen
H2O 51 0.52 0
 THE STRUCTURE OF CRYSTALLINE SOLIDS
 Crystal Structures
o Fundamentals
o Unit Cell
o Crystal Systems
o Metallic Crystal Structures
o Ceramic Crystal Structures
o Density Computations
o Polymorphism and Allotropy

 Crystallographic Points, Directions, and Planes

o Point Coordinates
o Crystallographic Directions 77
 THE STRUCTURE OF CRYSTALLINE SOLIDS
o Crystallographic Planes
o Linear and Planar Densities
o Close-Packed Crystal Structures

 Crystalline and Non-Crystalline Materials

o Single Crystals
o Polycrystalline Materials
o Polymorphism and Allotropy
o Determination of Crystal Structures: X-ray Diffraction
78
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystal Structures
 Solid materials may be classified according to the regularity with which
atoms or ions are arranged with respect to one another.
 A crystalline material is one in which the atoms are situated in a repeating
or periodic array over large atomic distances such that upon solidification,
the atoms will position themselves in a repetitive three-dimensional
pattern, in which each atom is bonded to its nearest-neighbour atoms.
 Levels of atomic arrangement in materials
o No order
o Short-range order
o Long-range order. 79
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystal Structures
Fundamentals
 Crystalline solids exhibit long-range order atomic arrangement
 Upon solidification, atoms position themselves in a repetitive three dimensional
pattern in which each atom is bonded to its nearest-neighbour atoms
 On solidification, all metals, most ceramic and a few polymeric materials form
crystal structures.
 In the absence of long range order, we have non-crystalline or amorphous
materials.
 Some properties of crystalline solids depend on the type of crystal structure it has.
 Crystal structure: is the manner in which atoms, ions or molecules of a solid are
spatially arranged. 80
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystal Structures

Fundamentals

 Atomic hard sphere model

 When describing crystals structures, atoms/ions as hard spheres

having well-defined diameters

 Spheres representing nearest neighbors touch each other

 Lattice -3 dimensional array of points coinciding with atomic

positions (sphere centers)

81
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystal Structures
Unit Cells
 A sub-structure of repeat entities that is used to represent the crystal
structure
 Building blocks of a crystal structure assuming the hard sphere model???
 Mostly parallelepipeds or prisms with 3 sets of parallel faces whose
corners coincide with atomic centers for convenience
 Shows a symmetry of the crystal with atom positions generated by
translation along it’s edges
82
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystal Structures
Fundamentals

Hard sphere unit cell representation (FCC)

Reduced-sphere unit cell (FCC)

Aggregate of many atoms (FCC) Eight unit cells put

together (SC) 83
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystal Structures
Fundamentals

84
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystal Structures
Crystal Systems
Example
 Determine the number of lattice points per cell in the cubic crystal
systems. If there is only one atom located at each lattice point, calculate
the number of atoms per unit cell.

85
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystal Structures
Crystal Systems
 There are so many possible crystal structures
 For convenience, we mostly group structures according to unit cell configurations
and/or atomic arrangements
 One method is by considering the unit cell geometry only
 7 possible combinations is possible each being a distinct crystal system
 x, y, z coordinate system is used with origin at one corner of the parallelepiped unit
cell corner
 Six parameters are used here to define a particular unit cell geometry called lattice
parameters
o a, b and c i.e. edge lengths and
o α, β, γ i.e. 3 interaxial angles 86
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystal Structures
Crystal system Axial relationship Interaxial angles

Cubic a = b= c 𝛼 = 𝛽 = 𝛾 = 90°

Tetragonal a=b≠c 𝛼 = 𝛽 = 𝛾 = 90°

Hexagonal a=b≠c 𝛼 = 𝛽 = 90°, 𝛾 = 120

Orthorhombic a≠b≠c 𝛼 = 𝛽 = 𝛾 = 90°

Rhombohedral (trigonal) a = b= c 𝛼 = 𝛽 = 𝛾 ≠ 90°

Monoclinic a≠b≠c 𝛼 = 𝛾 = 90°, ≠ 𝛽

Triclinic a≠b≠c 𝛼 ≠ 𝛽 ≠ 𝛾 ≠ 90°

87
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystal Structures
Crystal Systems
 Cubic system has 3

Simple Cubic Face Centred Cubic Body Centred

Cubic
 Tetragonal system has 2 structures

Simple Body Centred

Tetragonal Tetragonal 88
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystal Structures
Crystal Systems
 Hexagonal system has just 1 structure Hexagonal

 Orthorhombic system has 4 structures

Simple Body-Centred Base-Centred Face Centred

Orthorhombic Orthorhombic Orthorhombic Orthorhombic
89
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystal Structures
Crystal Systems
 Rhombohedral (trigonal) system has 1 structure

Rhombohedral

 Triclinic system has 1 structure  Monoclinic system has 2 structures

Triclinic Simple Base-Centred

90
Monoclinic Monoclinc
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystal Structures
Metallic Crystal Structures
 Atomic bonding type is metallic and non-directional
 Metals have minimal restriction as to the number and positions of nearest
neighbours hence dense atomic packing

1. Face-Centered Cubic (FCC) Crystal Structures

 Has Cubic geometry unit cell with the unit cell edge length denoted as a
 Each unit cell has effectively 4 atoms

NB: Since atoms are spherical, they have a well defined radius R 91
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystal Structures
Metallic Crystal Structures
 Relationship between unit cell edge length a and atomic/ionic radius R is

92
𝑎 = 2𝑅√2
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystal Structures
Metallic Crystal Structures
Features of FCC
 Unit cell volume (Vc) ???
 Volume of atom (Vs) ???

93
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystal Structures
Metallic Crystal Structures
Features of FCC
 Unit cell volume (Vc) ???
 Volume of atom (Vs) ???
 Atomic packing factor (APF) is 0.74 (Let’s calculate together)
 Coordination number is 12, i.e. nearest-neighbor/touching atoms

2. Body-Centered Cubic (BCC) Crystal Structures

 Has Cubic geometry unit cell with the unit cell edge length denoted as a
 Each unit cell has effectively 2 atoms
𝟒𝑹
 Relation between R and a is 𝒂 = 94
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystal Structures
Metallic Crystal Structures
Features of BCC
 Unit cell volume (Vc) ???
 Volume of atom (Vs) ???
 Atomic packing factor is 0.68
 Coordination number is 8, i.e. nearest-
neighbor/touching atoms

What do this diagrams

represent???
95
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystal Structures
Metallic Crystal Structures
Features of HCP
3. Hexagonal Close Packed (HCP)
Crystal Structures
 Has hexagonal prism geometry
 Each unit cell has effectively 6 atoms
 Atomic packing fraction is same as
that of FCC which is???
 Take a careful look at the atomic
positions and how they are shared
amongst other cells 96
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystal Structures
Metallic Crystal Structures
Features of Shared
HC P by 2
Shared by 6
 Coordination number is 12, i.e.
unit cells
unit cells
nearest-neighbor/touching atoms
 𝒄 𝒂 ratio mostly 1.633 but some
metals deviate slightly
 Belongs
𝑎 = 2𝑅to1
unit cell
 Atomic packing fraction (APF)???
 Unit cell volume, 𝑉𝐶 = 3𝑎𝑜2 𝑐𝑜 𝑐𝑜𝑠30°
 Prove that the APF of HCP is 0.74
97
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystal Structures - Metallic Crystal Structures
Crystal Atoms per
a versus R APF Examples
Structure unit cell

Simple cubic a = 2R 1 0.52 Polonium (Po), α-Mo

4𝑅 Fe, W, Mo, Nb, Ta, K,
BCC 𝑎= 2 0.68
√3 Na, V, Cr

FCC 𝑎 = 2𝑅√2 4 0.74 Cu, Au, Pt, Ag, Pb, Ni

Ti, Mg, Zn, Be, Co, Zr,

HCP a = 2R 6 0.74
Cd
98
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystal Structures
Crystal Atomic Crystal Atomic
Metal Metal
Structure Radius (nm) Structure Radius (nm)
Aluminium (Al) FCC 0.1431 Nickel (Ni) FCC 0.1246
Cadmium (Cd) HCP 0.1490 Platinum (Pt) FCC 0.1387
Chromium (Cr) BCC 0.1249 Silver (Ag) FCC 0.1445
Cobalt (Co) HCP 0.1253 Tantalum (Ta) BCC 0.1430
Copper (Cu) FCC 0.1278 Titanium (α) (Ti) HCP 0.1445
Gold (Au) FCC 0.1442 Tungsten (W) BCC 0.1371
Iron (α) (Fe) BCC 0.1241 Zinc (Zn) HCP 0.1332
Molybdenum (Mo) BCC 0.1363 Lead (Pb) FCC 0.1750
99
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystal Structures
Metallic Crystal Structures
Theoretical Density
 A knowledge of crystal structure of metals makes it possible for its theoretical
density to be calculated using the formula below:
𝑴𝒂𝒔𝒔 𝒐𝒇 𝒂𝒕𝒐𝒎𝒔 𝒊𝒏 𝒖𝒏𝒊𝒕 𝒄𝒆𝒍𝒍 (𝒏𝒖𝒎𝒃𝒆𝒓 𝒐𝒇 𝒂𝒕𝒐𝒎𝒔/𝒄𝒆𝒍𝒍)(𝒂𝒕𝒐𝒎𝒊𝒄 𝒎𝒂𝒔𝒔) 𝒏𝑨
𝝆= = =
𝑻𝒐𝒕𝒂𝒍 𝒗𝒐𝒍𝒖𝒎𝒆 𝒐𝒇 𝒖𝒏𝒊𝒕 𝒄𝒆𝒍𝒍 (𝒗𝒐𝒍𝒖𝒎𝒆 𝒐𝒇 𝒖𝒏𝒊𝒕 𝒄𝒆𝒍𝒍)(𝑨𝒗𝒐𝒈𝒂𝒅𝒓𝒐′ 𝒔 𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕) 𝑽𝒄 𝑵𝑨

n is number of atoms, A and NA are atomic weight and Avogadro’s number

respectively

Question
Cr has an atomic radius of 0.125 nm, a BCC crystal structure and atomic weight of
52.0 g/mol. Calculate its theoretical density (Measured density: 7.19 g/cm3). 100
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystal Structures
Metallic Crystal Structures • Ex: Cr (BCC)
Theoretical Density A = 52.00 g/mol
R = 0.125 nm
n = 2 atoms/unit cell

R a = 4R/√3 = 0.2887 nm
a
atoms
g
theoretical = 7.18 g/cm3 unit cell 2 52.00
mol
ractual = 7.19 g/cm3 =
a3 6.022 x 1023
volume atoms
unit cell mol 101
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystal Structures Metals/
Graphite/
Ceramics/ Polymers
Composites/
Alloys fibers
Metallic Crystal Structures 30
Semicond

Theoretical Density
B ased on data in Table B1, Callister
Platinum *GFRE, CFRE, & AFRE are Glass,
20 Gold, W
Carbon, & Aramid Fiber-Reinforced
 In general, metals > ceramics > polymers
Tantalum
Epoxy composites (values based on
60% volume fraction of aligned fibers

Why? 10 Silver, Mo in an epoxy matrix).

Cu,Ni
Steels

Metals have
Tin, Zinc
Zirconia
5

 (g/cm 3)
 Close-packing (metallic bonding) 4
Titanium
Al oxide
Diamond

 Often large atomic masses 3 Si nitride

Aluminum Glass -soda Glass fibers
Concrete
Ceramics have Silicon PTFE GFRE*
2 Carbon fibers
Magnesium G raphite
Silicone CFRE *
 Less dense packing PVC
PET
A ramid fibers
AFRE *
PC
 Often lighter elements
1 HDPE, PS
PP, LDPE

Polymers have
0.5
 low packing density (often amorphous) 0.4
Wood

 lighter elements 0.3

Data from Table B.1, Callister & Rethwisch, 8e.
102
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystal Structures
Polymorphism and Allotropy
 Some metals as well as non-metals and compounds can exhibit more than
one crystal structure
 The phenomenon is known as allotropy or polymorphism
 When it occurs in elemental solids, it is called allotropy while the term
polymorphism is used for compounds.
 The prevailing structure mostly depends on the temperature and the
external pressure
 Examples:
o BCC steel (iron) at room temperature which changes to FCC at 912 oC –
Allotropy
o In ZrO2 (monoclinic at room temperature transforms to tetragonal at 1170103oC and
then to the cubic at 2370 oC – Polymorphism
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystal Structures
Polymorphism and Allotropy
Example
Calculate the percent volume change as zirconia transforms from a tetragonal
to monoclinic structure. The lattice constants for the monoclinic unit cells are
a = 5.156, b = 5.191, and c = 5.304 Å, respectively. The angle for the
monoclinic unit cell is 98.9°. The lattice constants for the tetragonal unit cell
are a = 5.094 and c = 5.304 Å. Does the zirconia expand or contract during
this transformation? What is the implication of this transformation on the
mechanical properties of zirconia ceramics?

104
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystal Structures
Ceramic Crystal Structures
 Highly ionic ceramic materials contain cations and anions
 2 characteristics of the ions in crystalline ceramics influence their crystal
structure
a. Magnitude of the electrical charge on ions
b. Relative sizes of ions

 Magnitude of Electrical Charge

 Crystal must be electrically neutral (all positive charges must be balanced
by an equal number of negative charges)
 E.g. CaF2, Ca2+ is balanced by two F- ions 105
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystal Structures
Ceramic Crystal Structures
 Relative Sizes of Ions (rC and rA: Cation and anion radii)
𝑟𝐶
 is less than unity. Why???
𝑟𝐴

 Each cation prefers as many nearest-neighbor anions as possible and vice

versa
 Stable ceramic crystal structures form when anions surrounding a cation
are all in contact with it

106
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystal Structures
Ceramic Crystal Structures
 For a specific coordination number, there is a critical minimum rC/rA
ratio for which anion – cation contact is established
 Coordination number: number of anion nearest neighbour ions for a
cation and vice versa
Coordination Cation – Anion
 Coordination Nos and Geometries for Coordination
various rC/rGeometry
number Radius ratio A

2 < 0.155

3 0.155 – 0.225
107
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystal Structures
Ceramic Crystal Structures
 Coordination Nos and Geometries for various rC/rA
Coordination Cation – Anion
Coordination Geometry
number Radius ratio

4 0.225 – 0.414

6 0.414 – 0.732

8 0.732 – 1.000
108
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystal Structures
Ceramic Crystal Structures
Atomic Ionic Radius Atomic Ionic Radius
Cations Anions
Radius (nm) (nm) Radius (nm) (nm)
Aluminium Bromine(Br-) 0.1190 0.1960
0.1432 0.051
(Al3+)
Chlorine (Cl-) 0.0905 0.1810
Barium (Ba2+) 0.2176 0.134
Calcium (Ca2+) 0.1976 0.099 Fluorine (Fl-) 0.0600 0.1330
Cesium (Cs+) 0.2650 0.167 Iodine (I-) 0.1350 0.2200
Iron Fe 2+ (BCC) 0.1241 0.074 Oxygen (O2-) 0.0600 0.1350
Fe 3+ (FCC) 0.1269 0.064
Sulphur (S2-) 0.1060 0.1840
Potassium (K+) 0.2314 0.133
Nickel (Ni2+) Silicon (Si4+) 0.1176 0.1750
0.1243 0.1241
109
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystal Structures
Ceramic Crystal Structures
Example
 Show that the minimum cation-to-anion ratio for a coordination
number 3 is 0.155

111
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystal Structures
Ceramic Crystal Structures
Example
 Show that the minimum cation-to-anion ratio for a coordination
number 3 is 0.155

112
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystal Structures
Ceramic Crystal Structures – AX Type
 A is the cation which is equal in number to X anion in crystal
i. Rock Salt
ii. Cesium Chloride
iii. Zinc Blende
 Rock Salt structure

113
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystal Structures
Ceramic Crystal Structures – Rock Salt

 Coordination number for both ions is 6

 Cation-anion ratio is between 0.414 and 0.732

 Unit cell: FCC arrangement of anions with cation situated in body center
and each of 12 cell edge center

 E.g. NaCl, MgO, MnS, LiF, FeO

114
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystal Structures
Ceramic Crystal Structures
 Cesium Chloride structure
 Coordination number for both ions is 8
 Cation-anion ratio is between 0.732 and 1.000
 Unit cell: Anions located at each of the unit cell corners with one cation
in the body center
 Similar to BCC in metals
 E.g. CsCl

115
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystal Structures
Ceramic Crystal Structures
 Zinc Blende or Sphalerite Structure
 This has an AX structure with coordination number for both ions is 4
 Unit cell: Anions located at each of the unit cell corners and face
positions with the cation filling the interior tetrahedral positions.
 An equivalent structure results if Zn and S atom positions are reversed.
 E.g. ZnS

116
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystal Structures
Ceramic Crystal Structures
 AmXp Structure
 If the charges on the cations and anions are not the same, a compound can
exist with the chemical formula AmXp , where m and/or p 1.
 Coordination number of 8.
 Calcium ions are positioned at the centres of cubes, with fluorine ions at the
corners.
 The chemical formula shows that there are only half as many Ca2+ ions as F-
ions, and therefore the crystal structure would be similar to CsCl except that
only half the centre cube positions are occupied by Ca2+ ions.
117
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystal Structures
Ceramic Crystal Structures
 AmBnXp Structure
 It is also possible for ceramic compounds to have more than one type of
cation; for two types of cations (represented by A and B), their chemical
formula may be designated as AmBnXp.
 Barium titanate (BaTiO3), having both Ba2+ and Ti4+ cations, falls into this
classification.
 This material has a perovskite crystal structure and rather interesting
electromechanical properties.
 Ba2+ ions are situated at all eight corners of the cube and a single Ti4+ is at the
cube center, with O2- ions located at the center of each of the six faces.
 At temperatures above 120 C, the crystal structure is cubic. 118
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystal Structures
Ceramic Crystal Structures – Theoretical density
 Just like for metals, the theoretical density for ceramics is

n' = number of formula units within unit cell

∑AC = sum of the atomic weights of all cations in formula unit
∑A A = sum of the atomic weights of all cations in formula unit
VC = unit cell volume
N = Avogadro’s number
119
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystallographic Points, Directions and Planes
 Convention established in which 3 numbers/indices used to designate
point coordinates, directions and planes
 Basis for determining index values is
1. A unit cell
2. A right-handed coordinate system consisting of (x, y, z) axes with the
origin situated at one of the corners and the axes coinciding with the
unit cell edges
 Any point within the unit cell can be located
 This is located using the three point coordinate indices: q, r, and s.
 These indices are fractional multiples of the unit cell edge lengths; a, b
and c 120
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystallographic Points, Directions and Planes
 Convention established in which 3 numbers/indices used to designate
point coordinates, directions and planes
 Basis for determining index values is
1. A unit cell
2. A right-handed coordinate system consisting of (x, y, z) axes with the
origin situated at one of the corners and the axes coinciding with the
unit cell edges
 Any point within the unit cell can be located
 This is located using the three point coordinate indices: q, r, and s.
 These indices are fractional multiples of the unit cell edge lengths; a, b
and c 121
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystallographic Points, Directions and Planes
Point Coordinates
 q, r and s are the coordinates of point P in the unit cell
 q is a fraction of edge length a i.e. qa
 r is a fraction of edge length b i.e. rb
 s is a fraction of edge length c i.e. sc

 Note that by convention, the coordinates

of point P are written as q r s with values
less than or equal to unity
122
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystallographic Points, Directions and Planes
Point Coordinates
 For the unit cell shown below, locate the point having coordinates
1 1
1
4 2

123
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystallographic Points, Directions and Planes
Point Coordinates
 Specify the point coordinates of all atomic positions in a BCC unit cell
in tabular form.
The table must contain the following

124
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystallographic Points, Directions and Planes
Crystallographic Directions
 Directions are lines between two points, or a vector
 The following steps are used to determine the 3 directional indices:
1. A right-handed x-y-z coordinate system is first constructed. As a matter of
convenience, its origin may be located at a unit cell corner.
2. The coordinates of two points that lie on the direction vector (referenced to the
coordinate system) are determined—for example, for the vector tail, point 1: x1,
y1, and z1; whereas for the vector head, point 2: x2, y2, and z2.
3. Tail point coordinates are subtracted from head point components — that is, x2 –
x1, y2 – y1, and z2 – z1.
4. These coordinate differences are then normalized in terms of (i.e., divided by)
their respective a, b, and c lattice parameters—that is, 125
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystallographic Points, Directions and Planes
Crystallographic Directions
4. These coordinate differences are then normalized in terms of (i.e., divided by) their
respective a, b, and c lattice parameters – that is,
𝑥2 − 𝑥1 𝑦2 − 𝑦1 𝑧2 − 𝑧1
𝑎 𝑏 𝑐
which yields a set of three numbers
5. If necessary, these three numbers are multiplied or divided by a common factor to
reduce them to the smallest integer values.
6. The three resulting indices, not separated by commas, are enclosed in square brackets,
thus: [uvw]. The u, v, and w integers correspond to the normalized coordinate
differences referenced to the x, y, and z axes, respectively.

 In summary, the u, v, and w indices may be determined using the following

equations:
𝑥2 − 𝑥1 𝑦2 − 𝑦1 𝑧2 − 𝑧1
u=n ,v=n ,w=n 126
𝑎 𝑏 𝑐
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystallographic Points, Directions and Planes
Crystallographic Directions
Note:
 Negative indices are also possible, which are represented by a bar over the
appropriate index
o 1 1 1 has a negative component in the –y direction
 Changing the signs of all the indices produces an anti-parallel direction
o 1 1 1 is directly opposite to 1 1 1

 Some crystal structures have several nonparallel directions being equivalent

i.e. The spacing of atoms along each direction is the same
o E.g. 1 0 0 , 1 0 0 , 0 1 0 , 0 1 0 , 0 0 1 𝑎𝑛𝑑 0 0 1 are all equivalent
in cubic crystals
127
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystallographic Points, Directions and Planes
Crystallographic Directions
 Equivalent directions are grouped into a family, E.g., a family is written
as 100
 In cubic crystals, directions having the same indices without regard to
order or sign are equivalent
o E.g. ( 123 and 213 ) are equivalent.

The [100], [110] and [111]

directions within a unit cell
128
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystallographic Points, Directions and Planes
Crystallographic Directions
Example:
 Determine the indices of the direction shown below
Summary
x y z
Projections a/2 b 0c
Projections in terms of
½ 1 0
(a, b, c)
Reduction 1 2 0
Enclosure [1 2 0] 129
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystallographic Points, Directions and Planes
Crystallographic Directions
Example:
 Draw the 𝟏 𝟏 𝟎 direction within a cubic unit cell

130
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystallographic Directions

 Hexagonal Crystals

 A four-axis coordinate system otherwise called Miller-Bravais system is

employed

 Directional indices are denoted by 4 indices, as [u v t w]

 By convention, the first 3 indices pertain to the projections along the

a1, a2, a3 axes in the basal plane

 Conversion from a 3 index system to a 4 index system is achieved using

the following formulae
131
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystallographic Directions

 Hexagonal Crystals

 [ u' v ' w' ]  [ u v t w]

 Primed indices are associated with 3 index scheme

 Unprimed indices are associated with the Miller Bravais

 Four-index system [0 1 0] direction becomes 132

 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystallographic Directions

 Hexagonal Crystals

(a) (b) 133

 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystallographic Points, Directions and Planes
Crystallographic Planes
 The procedure used to obtain the h, k, l index numbers are as follows:
1. If the plane passes through the selected origin, either another
parallel plane is constructed within the unit cell by an appropriate
translation, or another origin is established at the corner of
another unit cell

134
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystallographic Points, Directions and Planes
Crystallographic Planes
2. At this point the plane either intersects or parallels each of the 3
axes; the length of the planar intercept for each of the axes is
determined in terms of the lattice parameters a, b and c
3. The reciprocals of these numbers are taken. A plane that parallels
an axis may be considered to have an infinite intercept, and,
therefore has a zero index
4. If necessary, the 3 numbers are changed to the set of smallest
integers by the multiplication or division by a common factor
135
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystallographic Points, Directions and Planes
Crystallographic Planes
5. Finally, the integer indices, not separated by commas, are
enclosed within parentheses, thus: (h k l)

 Intercepts on the negative axis has a bar over the particular index
 Reversing the directions of all indices specifies a plane parallel to, on
the opposite side of and equidistance from, the origin
 For cubic crystals, planes and directions with the same indices are
perpendicular to one another (who can show this using [1 0 0] and (1
0 0) ???) 136
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystallographic Points, Directions and Planes
Crystallographic Planes

 A family of planes contains all planes that are crystallographically

equivalent, i.e. have the same atomic packing and is designated by
indices enclose in braces, e.g., {100}

 Atomic Arrangements for Planes

 Atomic arrangement for a crystallographic plane depends on the type
of crystal structure
 Atoms here are represented by circles as would be obtained by a slice
through the center of a full-sized hard sphere 137
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystallographic Planes
Atomic Arrangements for (1 1 0) – FCC

138
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystallographic Planes
Atomic Arrangements for (1 1 0) – BCC

139
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystallographic Planes
Some Equivalent Planes

140
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystallographic Planes

 Example, in cubic crystals, the planes 1 1 1 , 1 1 1 , 1 1 1 , 1 1 1 ,

1 1 1 , 1 1 1 , 1 1 1 , and 1 1 1 all belong to the same family {1 1 1}

 Again in cubic systems, planes having the same indices, irrespective of

the order or sign are equivalent

 2 parallel planes are equivalent and have identical indices

141
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Summary
Crystallographic Planes x y z
Intercepts αa - b c/2
 Determine the miller indices of the
Intercepts in terms of
plane in the diagram shown below α -1 1/2
lattice parameters (a, b, c)
Reciprocals 1/α -1 2
Reduction (not necessary
here)
Enclosure 𝟎𝟏𝟐

142
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystallographic Planes
 Hexagonal Crystals

 A four-axis coordinate system otherwise called Miller-Bravais system is

employed also

 Plane indices are denoted by 4 indices, as (h k i l)

 i is some redundancy which is obtained by the sum of h and k through

i = - (h + k)

 Otherwise, h, k and l remains the same for both indexing systems i.e.
the 3-axis (x, y, z) system or the Miller-Bravais 4-axis system
143
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystallographic Planes
 Hexagonal Crystals

 Determine the Miller-Bravais indices of the plane shown in the

hexagonal unit cell below

144
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Linear Density – For Directions

 Linear density (LD) is defined as the number of atoms per unit length
whose centers lie on the direction vector for a specific crystallographic
direction, i.e.

𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑎𝑡𝑜𝑚𝑠 𝑐𝑒𝑛𝑡𝑒𝑟𝑒𝑑 𝑜𝑛 𝑑𝑖𝑟𝑒𝑐𝑡𝑖𝑜𝑛 𝑣𝑒𝑐𝑡𝑜𝑟

𝐿𝐷 =
𝑙𝑒𝑛𝑔𝑡ℎ 𝑜𝑓 𝑑𝑖𝑟𝑒𝑐𝑡𝑖𝑜𝑛 𝑣𝑒𝑐𝑡𝑜𝑟

 Units (e.g. nm-1, m-1)

145
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Linear Density

 Find the linear density for [1 1 0] within an FCC unit cell

146
 THE STRUCTURE OF CRYSTALLINE SOLIDS

Planar Density – For Planes

 Planar density (PD) is taken as the number of atoms per unit area that
are centered on a particular crystallographic plane, i.e.

𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑎𝑡𝑜𝑚𝑠 𝑐𝑒𝑛𝑡𝑒𝑟𝑒𝑑 𝑜𝑛 𝑝𝑙𝑎𝑛𝑒

𝑃𝐷 =
𝑎𝑟𝑒𝑎 𝑜𝑓 𝑝𝑙𝑎𝑛𝑒

 Units reciprocal area (e.g. nm-2, m-2)

147
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Planar Density

 Find the planar density of the (1 1 0) within an FCC unit cell

(110)

148
 THE STRUCTURE OF CRYSTALLINE SOLIDS

Linear and Planar Densities

 Linear density (LD) and planar density (PD) are important in the
process of slip which occurs in plastic deformation of metals

 Slip occurs on

o most densely packed crystallographic planes and

o in those planes, along the most dense crystallographic directions

(having the greatest atomic packing)

149
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystallographic Planes
Closed-Packed Crystal Structures

 The most efficient packing of equal sized spheres or atoms is that of

FCC or HCP with APF of 0.74

 These 2 crystal structures maybe described by closed-packed plane of

atoms

 FCC and HCP can be generated by stacking of these close-packed

planes

 Hence we have ABABABAB and ABCABCABCABC stacking sequence

 Difference arises from the stacking sequence 150

 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystallographic Planes
Closed-Packed Crystal Structures
 Starting Point  Hexagonal layer
 Three positions A (the first layer atomic positions), B & C (valleys) are shown
 The second layer (of hexagonal packing of atoms) can be positioned in valley B (or
equivalently in valley C)
Part of the hexagonal layer shown

Step-2

AB
Step-1
151
A
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystallographic Planes
Closed-Packed Crystal Layer-3
ABA
Structures (Option-1)
Continuing this
ABAB sequence we
C-site vacant
 The third layer can be get the HCP structure
Step-3
positioned with atoms
directly above the A
layer (Option-1) or with
atoms above the C layer
(Option-2) (Option-2)

ABC
Continuing this ABCABC
sequence we get the FCC structure
152
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystallographic Planes
Closed-Packed Crystal Structures
 HCP has ABABABABABAB stacking FCC crystals have ABCABCABCABC stacking
 For FCC, an atomic alignment repeats every third plane whiles for HCP, atomic
alignment repeats every second plane

HCP crystals FCC crystals 153

 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystalline Materials
Single Crystals
 In crystalline solids, when the periodic and repeated arrangement of
atoms extends throughout the entirety of the specimen, we have a single
crystal
 All the unit cells interlock and have the same orientation
 Single crystals exists naturally but can also be produced
artificially
 When a single crystal is allowed to grow without
constraint, it will assume a regular geometric shape
having flat surfaces Garnet single154crystal
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystalline Materials
Single Crystals
 Ordinarily difficult to grow because the environment must be carefully
controlled

Polycrystalline Materials
 Most crystalline solids have a composition of so many small crystals also
known as grains
 They are called polycrystalline materials
155
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystalline Materials
Polycrystalline Materials
 Formation of grains arises during the solidification process of the
polycrystalline specimen through the following processes:
i. Very small grains also called nuclei with random crystallographic orientations
develop at various sites in the initial stages

ii. The small grains grow by successive addition of atoms from the surrounding
liquid to the structure of each

iii. The extremities of adjacent grains impinge on each other as the solidification
process nears completion
156
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystalline Materials
Polycrystalline Materials
 Crystallographic orientation varies from grain to grain
 There is an atomic mismatch within the region where two grains meet.
This region/area is called grain boundary
(a) (b)

The schematic representation of

the formation of a polycrystalline
material is shown (NB: Square
grids depict unit cells)157
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystalline Materials
Polycrystalline Materials

(c) (d)

The schematic representation of

the formation of a polycrystalline
Photomicrograph of brass, 60
material is shown (NB: Square
grids depict unit cells) 158
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystalline Materials
Anisotropy
 Some single crystals have some of their physical properties depending on
the crystallographic direction along which the measurements were taken.
 A material property’s dependence on the crystallographic direction
along which it was measured is termed anisotropy
 It is associated with the variance in atomic or ionic spacing with
crystallographic direction
 So, what is isotropy???
160
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystalline Materials
Anisotropy
 The degree of anisotropy increases with decrease in structural
symmetry
 Triclinic structured materials are highly anisotropic, why???

a ≠ b ≠ c and α ≠ β ≠ γ

161
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystalline Materials
Anisotropy
 Polycrystalline materials Modulus of Elasticity (GPa)
- individual grains have Crystal
Structure
random crystallographic Metal [1 0 0] [1 1 0] [1 1 1]
orientation, hence
anisotropic Aluminum 63.7 72.6 76.1 FCC

 But the specimen Copper 66.7 130.3 191.1 FCC

composed of the grain Iron 125.0 210.5 272.7 BCC
aggregates behaves
isotropically Tungsten 384.6 384.6 384.6 BCC
162
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystalline Materials
Anisotropy
 The magnitude of the property measured represents some average of the
directional values
 Texture: The crystallographic orientation preferential nature of
polycrystalline materials

Crystalline silicon
dioxide (left) and
noncrystalline silicon
dioxide (right)
163
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystalline Materials
X-Ray Diffraction
 Information about the crystal structure of a material can be obtained by
using the x-ray diffraction technique
 When a beam of x-rays with single wavelength on the same order of
magnitude as the atomic spacing of a material strikes that material;

i. X-rays are scattered in all directions

ii. Most of the rays/radiations scattered by one atom are cancelled
out by that of other atoms
iii. However, x-rays that strike certain crystallographic planes at
specific angles are reinforced rather than annihilated 164
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystalline Materials
X-Ray Diffraction
 The phenomenon of reinforcement of scattered rays is known as
diffraction
 X-rays are diffracted (beam is reinforced) when Bragg’s law is satisfied by
conditions:
𝑛𝜆 = 2𝑑ℎ𝑘𝑙 sin 𝜃
o λ is the wavelength of the x-rays,
o θ is half the angle between the diffracted beam and original beam
o dhkl is the interplanar spacing between the planes that cause constructive reinforcement
of the beam
165
o n is the order of reflection (1, 2, 3, 4, ……)
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystalline Materials
Two waves (l and 2) that have
X-Ray Diffraction the same wavelength λ and
remain in phase after a
scattering event (waves 1ʹ and
2ʹ) constructively interfere with
one another. The amplitudes of
the scattered waves add
together in the resultant wave

Two waves (3 and 4) that have the same

wavelength λ and become out of phase after a
scattering event (waves 3ʹ and 4ʹ) destructively
interfere with one another. The amplitudes of 166
the two scattered waves cancel one another)
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystalline Materials
X-Ray Diffraction
 Bragg’s law: Relationship among λ, d and  for constructive interference

Diffraction of x-rays
by planes of atoms
(A–Aʹ and B–Bʹ)
𝑛𝜆 = 𝑆𝑄 + 𝑄𝑇 ⇒ 𝑛𝜆 = 𝑑ℎ𝑘𝑙 sin 𝜃 + 𝑑ℎ𝑘𝑙 sin 𝜃 = 2𝑑ℎ𝑘𝑙 sin 𝜃
 The magnitude of the distance between two adjacent and parallel planes of
atoms (i.e. dhkl) is a function of the Miller Indices as well as the lattice parameter
𝑎
 For crystal structures with cubic symmetry, 𝑑ℎ𝑘𝑙 = 167
ℎ2 +𝑘 2 +𝑙 2
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystalline Materials
X-Ray Diffraction
 Diffraction techniques – A common technique employs a powdered or
polycrystalline specimen
Schematic diagram of an x-ray diffractometer; T x-ray source, S
specimen, C detector, and O the axis around which the specimen
and detector rotate.

168
Diffraction pattern for powdered lead (Pb)
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystalline Materials

X-Ray Diffraction

 Question
For BCC Fe, its lattice parameter is 0.2866 nm. If a monochromatic radiation of
wavelength 0.1790 nm is used and the order of reflection is 1, compute
a) the interplanar spacing, and
b) the diffraction angle for the (2 2 0) set of planes.

 Solution
a)
a = 0.2866 nm 𝑎 0.2866 𝑛𝑚
𝑑ℎ𝑘𝑙 = = = 0.1013 𝑛𝑚
h = 2, k = 2, and l = 0 ℎ2 + 𝑘2 + 𝑙2 (2)2 +(2)2 +(0)2 169
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystalline Materials
X-Ray Diffraction
𝑛𝜆 (1)(0.1790 𝑛𝑚)
b) 𝑛𝜆 = 2𝑑ℎ𝑘𝑙 sin 𝜃  sin 𝜃 = = = 0.8840
2𝑑ℎ𝑘𝑙 (2)(0.1013 𝑛𝑚)
𝜃 = sin−1 0.8840 = 62.13°
The diffraction angle is 2 or 2 = (2)(62.13) = 124.26

Crystal Structure Identification

 From the diffraction patterns recorded, the orientation and quality of
the single crystal can be determined.
 The crystal structure can also be determined using the rotating crystal
and fixed wavelength x-ray source.
170
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystalline Materials
Crystal Structure Identification
 In SC metals, all possible planes will diffract, giving an h2 + k2 + l2
pattern of 1, 2, 3, 4, 5, 6, 8, ……
 In BCC metals, diffraction occurs only from planes having an even h2 +
k2 + l2 sum of 2, 4, 6, 8, 10, 12, 14, 16, ……
 For FCC metals, more destructive interference occurs, and planes having
h2 + k2 + l2 sums of 3, 4, 8, 11, 12, 16, …... will diffract.
 By calculating the values of sin θ and then finding the appropriate
pattern, the crystal structure can be determined for metals having one of
these simple structures 171
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystalline Materials
Crystal Structure Identification
 Example
The results of a x-ray diffraction experiment using x-rays with λ = 0.7107 Ǻ (a
radiation obtained from a molybdenum (Mo) target) show that diffracted peaks
occur at the following 2 angles:
Peak 2θ Peak 2θ
1 20.20 5 46.19
2 28.72 6 50.90
3 35.36 7 55.28
4 41.07 8 59.42
Determine the crystal structure, the indices of the plane producing each peak, and
the lattice parameter of the material. 172
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystalline Materials
Crystal Structure Identification
 We can first determine the sin2  value for each peak, then divide
through by the lowest denominator, 0.0308.
 Use 2 values for any sin𝟐 𝜽
Peak 2θ sin2 θ h2 +k2 + l2 (hkl)
of the peaks to 𝟎. 𝟎𝟑𝟎𝟖
calculate the inter-
1 20.20 0.0308 1 2 (110)
planar spacing and thus 2 28.72 0.0615 2 4 (200)
the lattice parameter. 3 35.36 0.0922 3 6 (211)
Picking peak 8: 4 41.07 0.1230 4 8 (220)
5 46.19 0.1539 5 10 (310)
𝑑400 =
𝜆
=
0.7107
= 0.7170 Å
6 50.90 0.1847 6 12 (222)
2 sin 𝜃 2 sin 29.71 7 55.28 0.2 152 7 14 (321)
8 59.42 0.2456 8 16 173
(400)
𝑎𝑜 = 𝑑400 ℎ2 + 0 + 0 = (7170 Å) 4 = 2.868 Å
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystalline Materials
Crystal Structure Identification
 Example
The figure shows the results of an x-ray diffraction
experiment in the form of the intensity of the
diffracted peak values, the 2 diffraction angle. If
x-rays with a wavelength of 0.15418 nm are used,
determine
a) the crystal structure of the metal;
b) the indices of the planes that produce each
of the peaks; and
c) the lattice parameter of the metal. 174
 THE STRUCTURE OF CRYSTALLINE SOLIDS
Crystalline Materials
Crystal Structure Identification
sin𝟐 𝜽
Peak 2θ sin2 θ h2 +k2 + l2 (hkl) dhkl Ao(hkl)
𝟎. 𝟎𝟐𝟑
1 17.5 0.023 1.000 3 (111) 0.507 0.878
2 20.5 0.032 1.368 4 (200) 0.433 0.867
3 28.5 0.061 2.618 8 (220) 0.313 0.886
4 33.5 0.083 3.589 11 (311) 0.268 0.887
5 35.5 0.093 4.016 12 (222) 0.253 0.876
6 41.0 0.123 5.300 16 (400) 0.220 0.880
7 45.0 0.146 6.328 19 (331) 0.201 0.878
8 46.5 0.156 6.734 20 (420) 0.196 0.873

a) The 3,4,8,11, . . . sequence means that the material is FCC

0.878+0.867+0.886+0.887+0.876+0.880+0.878+0.873
b) 𝑎𝑜 =
8
= 0.878 175