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The Structure of Crystalline Solids

ISSUES TO ADDRESS...
• How do atoms assemble into solid structures?
(focus on metals)

• How does the density of a material depend on

its structure?

• When do material properties vary with the

specimen orientation?

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 Reading
Chapter 3
– Section 3.1 Introduction
– Section 3.2 Fundamental Concepts
– Section 3.3 Unit Cells
– Section 3.4 Metallic Metal Structures (except the hexagonal close-packed crystal structure)
– Section 3.5 Density Computations
– Section 3.6 Polymorphism and allotropy
– Section 3.7 Crystal Systems
– Section 3.8 Point Coordinates
– Section 3.9 Crystallographic Directions (except directions in hexagonal systems)
– Section 3.10 Crystallographic Planes (except hexagonal crystals)
– Section 3.11 Linear and Planar Densities
– Section 3.12 Close-packed Crystal Structures
– Section 3.16 X-ray Diffraction
– Section 3.17 Noncrystalline Solids

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 Energy and Packing

• Non dense, random packing Energy

typical neighbor
bond length

typical neighbor r
bond energy

Energy

• Dense, ordered packing typical neighbor

bond length

typical neighbor r
bond energy

Dense, ordered packed structures tend to have lower energies.

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 Materials and Packing

Crystalline materials...
• atoms pack in periodic, 3D arrays
• typical of: -metals crystalline SiO2
-many ceramics Adapted from Fig. 3.22(a),
-some polymers Callister 7e.

Noncrystalline materials...
Si Oxygen
• atoms have no periodic packing
• occurs for: -complex structures
-rapid cooling

"Amorphous" = Noncrystalline
noncrystalline SiO2
Adapted from Fig. 3.22(b),
Callister 7e.
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 Unit cell

– Unit cell is that block of atoms which repeats itself to form space lattice.
– Materials arranged in short range order are called amorphous materials

Space Lattice

Unit Cell

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 Crystal Systems and Bravais Lattice

– Only seven different types of unit cells are necessary to create all point
lattices.

– According to Bravais (1811-1863) fourteen standard unit cells can

describe all possible lattice networks.

– The four basic types of unit cells are

 Simple
 Body Centered
 Face Centered
 Base Centered

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 7 Crystal Systems

Cubic Tetragonal Orthorhombic Monoclinic

a=b=c a=b≠c a≠b≠c a≠b≠c
α = β = γ = 90˚ α = β = γ = 90˚ α = β = γ = 90˚ α = β = 90˚ ≠ γ

Triclinic Rhombohedral Hexagonal

a≠b≠c a=b=c a=b≠c
α ≠ β ≠ 90˚ ≠ γ α = β = γ ≠ 90˚ α = β = 90˚ γ = 120˚
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 14 Bravais Lattices

S BC FC 2 FC
Cubic X X X
Tetragonal X X
Orthorhombic X X X X
Monoclinic X X
Triclinic X
Rhombohedral X
Hexagonal X

S = Simple: 1 atom at each corner of cell

BC = Body Centered: 1 atom at each corner of cell + 1 atom at the centre of the cell
FC = Face Centered: 1 atom at each corner of cell + 1 atom at the centre of each face
2FC = Base centered: 1 atom at each corner of cell + 1 atom in the centre of 2
faces opposing each other
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 Types of Unit Cells

– Cubic Unit Cell

 a=b=c
 α = β = γ = 900

Simple

Face centered Body Centered

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 Principal Metallic Crystal Structures

– 90% of the metals have either Body Centered Cubic (BCC), Face Centered Cubic (FCC) or
Hexagonal Close Packed (HCP) crystal structure.
– HCP is denser version of simple hexagonal crystal structure.

BCC Structure FCC Structure HCP Structure

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 Body Centered Cubic (BCC) Crystal Structure

– Represented as one atom at each corner of cube and one at the center of cube.
– Each atom has 8 nearest neighbors.
– Therefore, coordination number is 8.
– Examples :
 Chromium (a = 0.289 nm)
 Iron (a = 0.287 nm)
 Sodium (a = 0.429 nm)

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 Body Centered Crystal Structure

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 BCC Crystal Structure (Cont..)

– Each unit cell has eight 1/8 atom at corners

and 1 full atom at the center.
– Therefore each unit cell has

(8x1/8 ) + 1 = 2 atoms
– Atoms contact each other at cube diagonal

Therefore, a = 4R

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 Atomic Packing Factor of BCC Structure

Volume of atoms in unit cell

Atomic Packing Factor =
Volume of unit cell

 4 ΠR 3 
Vatoms = 2.  = 8.373R3
 
 3 
3
 4R 
V unit cell = a3 =   = 12.32 R3
 
 3 

8.723 R3 = 0.68
Therefore APF = 12.32 R3

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 Face Centered Cubic (FCC) Crystal Structure

– FCC structure is represented as one atom each at the corner of cube and at the center of each cube
face.
– Coordination number for FCC structure is 12
– Atomic Packing Factor is 0.74
– Examples :-
 Aluminum (a = 0.405)
 Gold (a = 0.408)

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 Face centered crystal Structure

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 FCC Crystal Structure (Cont..)

– Each unit cell has eight 1/8 atom at corners and six ½ atoms at
the center of six faces.
– Therefore each unit cell has

(8 x 1/8)+ (6 x ½) = 4 atoms

– Atoms contact each other across cubic face diagonal

Therefore, lattice 4R
constant a =
2

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 Simple Cubic Crystal Structure

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 Question Time

– Calculate the atomic packing factor of a simple cubic cell

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 Hexagonal Close-Packed Structure

A sites
c Top layer
B sites
Middle layer
A sites
a Bottom layer

• Coordination # = 12
• APF = 0.74
6 atoms/unit cell
• c/a = 1.633 ex: Cd, Mg, Ti, Zn

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 Theoretical Density, ρ

Mass of Atoms in Unit Cell

Density = ρ =
Total Volume of Unit Cell

nA
ρ =
V C NA

where n = number of atoms/unit cell

A = atomic weight
VC = Volume of unit cell = a3 for cubic
NA = Avogadro’s number
= 6.023 x 1023 atoms/mol

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 Theoretical Density for FCC Metals: Example of Copper

Atomic radius R= 0.128 nm

Atomic weight A= 63.5 g/mol
Number of atoms per unit cell n=4 atoms/unit cell
Volume of unit cell Vc= a3= 16√2 R3

Mass of Atoms in Unit Cell

Density = ρ =
Total Volume of Unit Cell

nA = 4 atoms / unit cell × 63.5 g / mol

ρ =
VC NA 16 2 (0.128 ×10 −7 cm )3 / unit cell × 6.023 ×10 23 atoms / mol

ρ = 8.89 g/cm3
Experimentally, the density of copper was found to be equal to 8.94 g/cm3
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Question Time: Theoretical density of BCC Metals – Example of Molybdenum

Mo crystallises in a BCC structure, its atomic radius is equal

to 0.136 nm and its atomic weight is 95.94 g/mol. Calculate
its theoretical density.

Experimentally the density of Mo is equal to 10.22 g/cm3

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 Densities of Material Classes
Graphite/
In general Metals/
Ceramics/ Polymers
Composites/
ρmetals > ρceramics > ρpolymers 30 Alloys
Semicond
fibers
Based on data in Table B1, Callister
Why? 20 Platinum
Gold, W *GFRE, CFRE, & AFRE are Glass,
Carbon, & Aramid Fiber-Reinforced
Metals have... Tantalum
Epoxy composites (values based on
60% volume fraction of aligned fibers
• close-packing 10 Silver, Mo in an epoxy matrix).
Cu,Ni
(metallic bonding) Steels
Tin, Zinc
• often large atomic masses 5
Zirconia

ρ (g/cm3 )
Ceramics have... 4
Titanium
Al oxide
Diamond
Si nitride
• less dense packing 3
Aluminum Glass -soda Glass fibers
Concrete
• often lighter elements 2 Silicon PTFE GFRE*
Carbon fibers
Magnesium Graphite
Polymers have... Silicone
PVC
CFRE*
Aramid fibers
AFRE*
PET
• low packing density 1 PC
HDPE, PS
(often amorphous) PP, LDPE

• lighter elements (C,H,O) 0.5

Wood
Composites have... 0.4
0.3
• intermediate values Data from Table B1, Callister 7e.
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 Polymorphism or Allotropy

– Metals exist in more than one crystalline form. This is caller polymorphism or
allotropy.
– Temperature and pressure leads to change in crystalline forms.
– Example:- Iron exists in both BCC and FCC form depending on the temperature.

Liquid
Iron

-2730C 9120C 13940C 15390C

α Iron γ Iron δ Iron

BCC FCC BCC
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 Point Coordinates
z Point coordinates for unit cell center are
111
a/2, b/2, c/2 ½½½
c
Point coordinates for unit cell corner are 111

000
y
a b Translation: integer multiple of lattice constants 
identical position in another unit cell
x •
z 2c
•

• •
b y
b
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 Crystallographic Directions

z Algorithm
1. Vector repositioned (if necessary) to pass
through origin.
2. Read off projections in terms of
unit cell dimensions a, b, and c
y 3. Adjust to smallest integer values
4. Enclose in square brackets, no commas

x [uvw]

ex: 1, 0, ½ => 2, 0, 1 => [ 201 ]

-1, 1, 1 => [ 111 ] where overbar represents a
negative index
families of directions <uvw>
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 Linear Density

– Linear Density of Atoms ≡ LD = Number of atoms

Unit length of direction vector
[110]
ex: linear density of Al in [110]
direction
a = 0.405 nm

# atoms
a 2
LD = = 3.5 nm −1
length 2a

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 Question Time

Determine the linear density of the following directions in a BCC unit cell:
1) 100
2) 110
3) 111

If the material is iron with R = 0.124 nm, calculate the linear densities

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 Crystallographic Planes

Adapted from Fig. 3.9, Callister 7e.

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 Crystallographic Planes

– Miller Indices: Reciprocals of the (three) axial intercepts for a plane, cleared of
fractions & common multiples. All parallel planes have same Miller indices.

– Algorithm
1. Read off intercepts of plane with axes in
terms of a, b, c
2. Take reciprocals of intercepts
3. Reduce to smallest integer values
4. Enclose in parentheses, no
commas i.e., (hkl)

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 Crystallographic Planes

example a b c
z
1. Intercepts 1 1 ∞
c
2. Reciprocals 1/1 1/1 1/∞
1 1 0
3. Reduction 1 1 0
y
4. Miller Indices (110) a b
x z
example a b c
1. Intercepts 1/2 ∞ ∞ c
2. Reciprocals 1/½ 1/∞ 1/∞
2 0 0
3. Reduction 1 0 0
y
4. Miller Indices (100) a b
x
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 Crystallographic Planes

z
example a b c c
1. Intercepts 1/2 1 3/4 •
2. Reciprocals 1/½ 1/1 1/¾
2 1 4/3 • y
•
3. Reduction 6 3 4 a b

4. Miller Indices (634) x

Family of Planes {hkl}

Ex: {100} = (100), (010), (001), (100), (010), (001)

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 Planar Density

number of atoms centred on a plane

PD =
area of plane

For FCC unit cell

1
PD111 = 2
2 3R
1
PD100 = 2
4R
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Crystallographic Planes

– We want to examine the atomic packing of

crystallographic planes
– Iron foil can be used as a catalyst. The atomic packing of
the exposed planes is important.

a) Draw (100) and (111) crystallographic planes for Fe.

b) Calculate the planar density for each of these planes.

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 Planar Density of (100) Iron

Solution: At T < 912°C iron has the BCC structure.

2D repeat unit

(100) 4 3
a= R
3

Adapted from Fig. 3.2(c), Callister 7e. Radius of iron R = 0.1241 nm

atoms
2D repeat unit 1
1 atoms atoms
Planar Density = = 2 = 12.1 = 1.2 x 1019

area a2 4 3 nm 2 m2
R
2D repeat unit 3
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 Planar Density of (111) Iron

Solution (cont): (111) plane 1 atom in plane/ unit surface cell

2a atoms in plane
atoms above plane
atoms below plane

3
h= a
2
2
 4 3  16 3 2
area = 2 ah = 3 a = 3 
2
R÷
÷ = R
atoms  3  3
2D repeat unit 1
atoms = atoms
Planar Density = = 7.0 0.70 x 1019
area 16 3 2
nm 2 m2
R
2D repeat unit 3
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 X-Ray Diffraction

– Diffraction gratings must have spacings comparable to the wavelength of diffracted

radiation.
– Can’t resolve spacings < λ
– Spacing is the distance between parallel planes of atoms.

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 X-Rays to Determine Crystal Structure

• Incoming X-rays diffract from crystal planes.

reflections must
be in phase for
a detectable signal
extra
distance
λ Adapted from Fig. 3.19,
travelled θ θ Callister 7e.
by wave “2” spacing
d between
planes

Measurement of X-ray
intensity nλ
critical angle, θc, d=
(from 2 sin θc
allows computation of
detector)
planar spacing, d.
θ
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 X-Ray Diffraction Pattern
z z z
c c c
(110)
y y y
a b a b a b
Intensity (relative)

x x x (211)

(200)

Diffraction angle 2θ

Diffraction pattern for polycrystalline α-iron (BCC)

Adapted from Fig. 3.20, Callister 5e.

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 Question Time

– Using the first peak in the previous diffraction diagram, calculate the lattice
parameter a for BCC iron.

– Hint: for cubic materials we have the following relation between interplanar
spacing d and lattice parameter a:

a
d hkl =
2 2 2
h +k +l

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 Amorphous Materials

– Random spatial positions of atoms

– Polymers: Secondary bonds do not allow formation of parallel and tightly packed chains
during solidification.
 Polymers can be semicrystalline.
– Glass is a ceramic made up of SiO4 4- tetrahedron subunits – limited mobility.
– Rapid cooling of metals (10 8 K/s) can give rise to amorphous structure (metallic glass).
– Metallic glass has superior metallic properties.

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 SUMMARY

• Atoms may assemble into crystalline or

amorphous structures.
• Common metallic crystal structures are FCC, BCC, and
HCP. Coordination number and atomic packing factor
are the same for both FCC and HCP crystal structures.
• We can predict the density of a material, provided we
know the atomic weight, atomic radius, and crystal
geometry (e.g., FCC, BCC, HCP).
• Crystallographic points, directions and planes are
specified in terms of indexing schemes.
Crystallographic directions and planes are related
to atomic linear densities and planar densities.

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