MSE 1101: Introduction to

Materials Science and

Engineering
 Lec 05: Packing of Atoms in
Solids

Topics to Cover
❑ Atomic Arrangement in Solids
❑ Principles of Atomic Packing
❑ Introduction to Crystallography
❑ Crystalline and Non-crystalline Materials
❑ Atomic Packing in Ceramics and Polymers

References
1. Ashby and Jones. Engineering Materials 1, 3rd Ed, Ch05, pp.67-82.
2. Callister & Rethwisch. Materials Science and Engineering: An Introduction, 9th Ed, Ch03, pp.51-104.
 Atomic Arrangement in Solids
❑ Many engineering materials (almost all metals and ceramics, for
instance) are made up entirely of small crystals (also known as
grains)
• where atoms are packed in regular, repeating, three-dimensional patterns
• the grains are stuck together, meeting at grain boundaries

❑ An individual crystal can best be understood by thinking of atoms as

hard spheres (although, this is a big simplification!)

❑ To make things even simpler, for the moment consider a material that
is pure—with only one size of hard sphere—which has nondirectional
bonding, so we can arrange the spheres subject only to geometrical
constraints.
• pure copper is a good example of a material satisfying these conditions.
 Concept of ordering
No order Short-range order
❑ No regular relationship between ❑ Special arrangement of atoms extends only to
atoms the atom’s nearest neighbours

❑ Atoms randomly fill up the space ❑ Each water molecule has a short-range order
to which it is confined between H and O atoms, but each water
molecule has no special arrangement but
❑ Example: monatomic gases instead randomly fill up the space available to
them.
❑ Similar situation exists in ceramic glasses and
non-crystalline polymers
 Long-range order
❑ Atoms rearrange themselves in an identical,
regular, repetitive three-dimensional grid-like
pattern, called a lattice.
❑ Lattice is a collection of points, arranged in a
periodic pattern so that the surroundings of
each lattice point in the lattice are identical.
❑ Each atom has both short-range order, since
the surroundings of each lattice points are
identical, and long-range order, since the
lattice extends periodically throughout the
entire material.
❑ A lattice differs in both shape and size A Lattice
from material to material, depending on
the size of atoms and the type of bonding
between the atoms.
 Crystalline Solids
⚫ when atoms are arranged in both short- and
long-range ordered, repetitive
three-dimensional, geometric arrangement, a
crystal is formed
⚫ common in metallic, ceramic and some
polymeric materials

Non-crystalline, or Amorphous Solids

⚫ atoms arranged in random, short-range
ordered, non-repetitive arrangement
crystalline and amorphous
⚫ common in glassy and some metallic
form of silica
materials due to complex chemistry and
rapid cooling
 silicon single crystal

Liquid crystal display

amorphous but can undergo localized crystallization
in response to an external electric field
polycrystalline stainless steel
showing grains and grain boundaries
 Classification of materials
based on the type of atomic order

Monatomic Gases Liquid Crystals Crystalline Materials

No order Long-range order and Short and long-range order
Example: Argon gas short-range order in
small volumes
Examples: LCD Polymers

Single Crystals
Amorphous Materials
Examples: Si, GaAs
No long-range order,
only short-range order
Poly Crystals
Examples: Amorphous Si,
Examples: Metals & alloys,
Glasses, Plastics
and most Ceramics
 Introduction to Crystallography
❑ Crystallography is the experimental science of determining the arrangement of atoms in
crystalline solids

❑ Crystallographic methods depend on analysis of the diffraction patterns of a sample

targeted by a beam of some type.
• X-rays are most commonly used; other beams used include electrons or neutrons.
 Lattice and the unit cell

⚫ Lattice - A collection of points that divide 3D space into

smaller equally sized segments.

⚫ Unit cell - A sub-division of the lattice that still retains the

overall characteristics of the entire lattice, and stacked together
endlessly to form the lattice.

⚫ Atomic radius - The apparent radius of an atom, typically

calculated from the dimensions of the unit cell, using
close-packed directions (depends upon coordination number).

⚫ Packing factor - The fraction of space in a unit cell occupied by

atoms
 unit cell - the basic structural unit or
building block of the crystal structure
defines the crystal structure by virtue
of its geometry and the atom
positions within

Unit cell parameters

• dimensions (a, b, c)
• angles (α, β, γ)
Characteristics of Seven Crystal Systems
The fourteen types of Bravais lattices grouped in seven crystal systems.
 Metallic Crystal Structures

Face-Centred Cubic (FCC)

Cu ,Al, Au,Ag

Hexagonal Closed Pack (HCP)

Body-Centred Cubic (BCC)

 Example: Unit cell properties of FCC

Coordination Number
= Total number of neighbours of an atom
= 6 corner atoms + 6 face-centred atoms
= 12 atoms

Number of atoms / cell

= 8 atoms in each corners x Each shared by 8 cells
+ 6 atoms at the face x Each shared by 2 cells
= 4 atoms / cell
The APF is the sum of the sphere volumes of all atoms
within a unit cell (assuming the atomic hard sphere
model) divided by the unit cell volume—that is
 Unit cell properties: A Summary

Lattice Co- Number of Atomic

Parameter ordination Atoms per Packing
Number Unit Cell Factor

SC a=2R 6 1 0.52
BCC a = (4/√3) 8 2 0.68
R
FCC a = (2√2) R 12 4 0.74
a=2R
HCP 12 6 0.74
c = 1.633 a
Atomic Packing
Factor 4R

a
volume of atoms in unit cell
APF =
volume of unit cell a

(volume of atom) x (number of atom /cell)

=
volume of unit cell
a = lattice parameter
(4/3 π R3) x (4) 16/3 π R3 R = atomic radius
= =
3 (2√2R)3
a (4R)2 = a2 + a2
= 0.74 a = 2√2 R

Therefore, the atomic packing factor of FCC unit cell is 74%.

 Theoretical bulk density of crystals

mass of an atom
(g)
# atoms / unit atomic weight
cell (g/mol)

nM nA
ρ=
mass of atoms = =
cell volume VC VC
NA

volume / unit Avogadro’s number

cell (cm3/unit (6.023 x 1023 atoms/mol)
cell)
Example: Determining the Density of FCC Copper
𝑛𝐴
Copper has an atomic radius of 0.128 nm, an FCC crystal 𝜌=
structure, and an atomic weight of 63.5 g/mol. Compute its bulk 𝑉 𝐶 𝑁𝐴
density.

n ACu n ACu n ACu

ρ=
VC N A
= 3 = (2√2 r)3 NA
a NA

[ 4 atoms/cell ] x [ 63.5 g/mol ]

[2√2 (1.28x10-8) cm3/ unit cell ]3 x [ 6.023x1023 atoms/mol ]

= 8.89 g/cm3
 ρ ρ ρ
Why metals
>
ceramics
> ?
polymers

Metals have …
• Close-packing (metallic bonding)
• Large atomic masses

Ceramics have …
• Less dense packing (covalent bonding)
• Often lighter elements (oxygen, carbon)

Polymers have …
• Poor packing (often amorphous)
• Lighter elements (carbon, hydrogen)

Composites – average values

 Principles of Atomic Packing
❑ Many crystals structures can be
described as stacking
arrangements atoms in 2-D
lattices or, nets.

❑ Structures based on the square

net
•Simple cubic (SC)
•Body-centred cubic (BCC)

❑ Structures based on the closed-packed net has the more efficient packing

close-packed net
•Face-centred cubic (FCC)
•Hexagonal close-packed (HCP)
Packing sequence of structures based on close-packed net

1. Bottom layer : “A”

2. Place successive layer over
the “B” or “C” positions
 Layers stacked as
ABCABC...
resulting FCC structure

Layers stacked as
ABABAB...
resulting HCP
structure
 B B
C C
B B B
C C C
B B
C C
Face-Centred Cubic (FCC) Cell
Hexagonal Close-Packed (HCP) Cell
Hexagonal Close-Packed (HCP) Cell Face-Centred Cubic (FCC) Cell
Why should Al choose to be FCC Why are we interested in
while Mg chooses to be HCP? packing sequence of crystals?

❑ The answer to this is that materials choose the ❑ It is easier for crystal lattice deformation to
crystal structure that gives minimum energy. occur in the direction that is close packed.

❑ The difference in energy between alternative ❑ The number and direction of close-packed
structures is often slight. planes vary according to packing sequence
of crystal.
• Because of this, the crystal structure that
gives the minimum energy at one
temperature may not do so at another.
• Thus, tin changes its crystal structure if it is
cooled enough; and, incidentally, becomes
much more brittle in the process.
 Crystalline and Noncrystalline Materials

Single Crystals

❑ When repeated arrangement of atoms in a crystalline

solid extends throughout the entirety of the specimen
without interruption, the result is a single crystal.
• Exists in nature, but can also be produced artificially with difficulty
using carefully controlled environment

• When single crystal grows, it assumes a regular geometric shape

having flat faces
garnet single crystal turbine blades

❑ Within the past few years, single crystals have become ❑ Engineering applications requiring single crystals:
extremely important in many of our modern technologies. • Gems
• Diamond single crystals for abrasives
• Ni-base alloys single crystals for turbine blade
 Polycrystals
❑ Most crystalline solids are composed of a
collection of many small crystals or grains.
❑ Such materials are termed polycrystalline.

❑ Each grain is itself is a single crystal, which

is typically range from 1 nm to 2 cm (from a
few to 108 atomic layers).

❑ Many small crystals or nuclei having random crystallographic

orientations form at various positions during solidification.

Nb-Hf-W plate with an electron beam weld ❑ There exists some atomic mismatch within the region where
two grains meet; this area is called a grain boundary.
 Anisotropy
❑ Many properties of single crystal (elastic modulus, ❑ Properties of polycrystal may or may not vary
electrical conductivity, refractive index, etc.) of some with direction.
substance vary with crystallographic direction.
❑ For randomly oriented grains (resulted during
❑ These directionality of properties is termed anisotropy. casting, for example), properties are “isotropic”.
• associated with the variance of atomic or ionic spacing
with crystallographic direction. ❑ If grains are textured (after rolling, forging, etc.),
anisotropy resulted.
❑ Substances having properties independent of the
direction of measurement are isotropic.

BCC iron
single crystal
E = 125 GPa textured structure with elongated
grains, resulting anisotropic
properties along longitudinal and
E = 272 GPa casting with uniform grains, transverse direction of rolling
resulting isotropic properties
 Polymorphic and allotropic transformations

❑ Some materials may exist in more than one crystal

structure in the solid state. This is called polymorphism.
• Example: Iron, carbon, steels, silica, zirconia.

❑ If the material is an elemental solid, it is called allotropic

369/3
2
material.
• Example: Fe, C.

❑ The mechanisms and kinetics of the phase

transformation (in the solid state) is vitally important in
materials science and engineering for modifying the
properties of material.
 Atomic Packing in Ceramics and Polymers

Ceramic structures

❑ Generally complex, since the material

contains more than one element, usually a
small cation and a large anion

❑ Simple structures may also form,

e.g. rocksalt structure of NaCl rocksalt structure

❑ When two species of atoms are not in the

ratio 1 : 1, as in compounds like the nuclear
fuel UO2 (a ceramic too) the structure
becomes more complicated. UO2 BaTiO3

❑ Structures having more than two elements

are even further complicated
 Glass structures

❑ All silica-based ❑ Modifiers (e.g., Al, Na) are added

glass structures to open up / break the network
are based on and reduce the melting point
SiO44- tetrahedron SiO44- tetrahedron

❑ Si-O bonding is
largely covalent, but
overall SiO4-4 block
has charge of -4.
❑ Various silicate
structures are formed
by different ways of
arranging SiO44- blocks. Atom packing in Addition of soda breaks up the bonding
amorphous (glassy) silica in amorphous silica, giving soda glass
 Polymer structures
❑ Polymers are much more complex
structurally than metals

❑ Polymers are huge chain-like

molecules (huge, that is, by the
standards of an atom) in which the
atoms forming the backbone of the
chain are linked by covalent bonds.

❑ Molecules such as these form long,

flexible, spaghetti-like chains

The three–dimensional appearance of How the molecules are packed

a short bit of a polyethylene molecule together in polymers
Large molecular weight polyethylene
 Any
Question?