The Structure of Crystalline Solids

The properties of materials are

directly related to their crystal
structure.
e.g. magnesium and beryllium
are brittle - gold is not

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

• How does the density of a material depend on

its structure?

• When do material properties vary with the

sample (i.e., part) orientation?
Chapter 3 – Structure of crystalline solids
 Energy and Packing
• Non dense, random packing Energy

typical neighbour
bond length

typical neighbour r
bond energy

• Dense, ordered packing Energy

typical neighbour
bond length

typical neighbour r
bond energy

Dense, ordered packed structures tend to have lower

energies.
Chapter 3 – Structure of crystalline solids
 Materials and Packing
Crystalline materials...
• atoms pack in periodic, 3D arrays
• typical of: -metals
-many ceramics
-some polymers crystalline SiO2

Si Oxygen
Noncrystalline materials...
• atoms have no periodic packing
• occurs for: -complex structures
-rapid cooling
"Amorphous" = Noncrystalline noncrystalline SiO2

Chapter 3 – Structure of crystalline solids

Copper Block-copolymer

http://www.dur.ac.uk/mark.wilson/research.html
Chapter 3 – Structure of crystalline solids
 Section 3.3 – Crystal Systems
Unit cell: smallest repetitive volume which
contains the complete lattice pattern of a crystal.

7 crystal systems

14 crystal lattices

a, b, and c are the lattice constants

Fig. 3.4, Callister 7e.

Chapter 3 – Structure of crystalline solids

Unit cell are
parallelpipeds or
prisms with 3 sets
of parallel faces
The corners of the
unit cell coincide
with the centre of
atoms.

Chapter 3 – Structure of crystalline solids

 Section 3.4 – Metallic Crystal Structures
• How can we stack metal atoms to minimize
empty space?
2-dimensions

vs.

Now stack these 2-D layers to make 3-D structures

Chapter 3 – Structure of crystalline solids

 Metallic Crystal Structures
• Tend to be densely packed.
• Reasons for dense packing:
- Typically, only one element is present, so all atomic
radii are the same.
- Metallic bonding is not directional.
- Nearest neighbour distances tend to be small in
order to lower bond energy.
- Electron cloud shields cores from each other
• Have the simplest crystal structures.

We will examine three such structures...

Chapter 3 – Structure of crystalline solids

 Simple Cubic Structure (SC)
• Rare due to low packing density (only Po has this structure)
• Close-packed directions are cube edges.

• Coordination # = 6
(# nearest neighbors)

Chapter 3 – Structure of crystalline solids

 Atomic Packing Factor (APF)
Volume of atoms in unit cell* Volume of a sphere:
APF = 4
𝑉𝑉𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠 = 𝜋𝜋𝑅𝑅 3
Volume of unit cell 3
Volume of a cube:
*assume hard spheres 𝑉𝑉𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 = 𝑎𝑎3

• APF for a simple cubic structure = 0.52

volume
atoms atom
a 4
unit cell 1 π (0.5a) 3
3
R=0.5a APF =
a3 volume
close-packed directions
unit cell
contains 8 x 1/8 = 1 atom/unit cell

Chapter 3 – Structure of crystalline solids

Body Centered Cubic Structure (BCC)
• Atoms touch each other along cube diagonals.
--Note: All atoms are identical; the center atom is shaded
differently only for ease of viewing.

ex: Cr, W, Fe (α), Tantalum, Molybdenum

• Coordination # = 8

2 atoms/unit cell: 1 center + 8 corners x 1/8

Chapter 3 – Structure of crystalline solids

 Atomic Packing Factor: BCC

• APF for a body-centered cubic structure = 0.68

Chapter 3 – Structure of crystalline solids

 Face Centered Cubic Structure (FCC)
• Atoms touch each other along face diagonals.
--Note: All atoms are identical; the face-centered atoms are shaded
differently only for ease of viewing.

ex: Al, Cu, Au, Pb, Ni, Pt, Ag

• Coordination # = 12

Adapted from Fig. 3.1, Callister 7e.

4 atoms/unit cell: 6 face x 1/2 + 8 corners x 1/8

(Courtesy P.M. Anderson)
Chapter 3 – Structure of crystalline solids
 Atomic Packing Factor: FCC

• APF for a face-centered cubic structure = 0.74

maximum achievable APF

Chapter 3 – Structure of crystalline solids

 FCC Stacking Sequence
• ABCABC... Stacking Sequence
• 2D Projection
B B
C
A
A sites B B B
C C
B sites B B
C sites

A
• FCC Unit Cell B
C

Chapter 3 – Structure of crystalline solids

 Hexagonal Close-Packed Structure
(HCP)
• ABAB... Stacking Sequence
• 3D Projection • 2D Projection

A sites Top layer

c
B sites Middle layer

A sites Bottom layer

a

• Coordination # = 12 6 atoms/unit cell

• APF = 0.74 ex: Cd, Mg, Ti, Zn
• c/a = 1.633
Chapter 3 – Structure of crystalline solids
HCP FCC

Chapter 3 – Structure of crystalline solids

 Theoretical Density, ρ

Mass of Atoms in Unit Cell

Density = ρ =
Total Volume of Unit Cell

nA
ρ =
VC 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

Chapter 3 – Structure of crystalline solids

 Theoretical Density, ρ
• Ex: Cr (BCC)
A = 52.00 g/mol
R = 0.125 nm
n=2
R
a a = 4R/ 3 = 0.2887 nm

atoms
g
unit cell 2 52.00 ρtheoretical = 7.18 g/cm3
mol
ρ= ρactual = 7.19 g/cm3
a3 6.023 x 1023
volume atoms
unit cell mol
Chapter 3 – Structure of crystalline solids
 Densities of Material Classes
In general Metals/
Graphite/
Composites/
ρmetals > ρceramics > ρpolymers Alloys
Ceramics/
Semicond
Polymers
fibers
30
Why? Platinum
Based on data in Table B1, Callister
20 Gold, W *GFRE, CFRE, & AFRE are Glass,
Metals have... Tantalum Carbon, & Aramid Fiber-Reinforced
Epoxy composites (values based on
• close-packing 60% volume fraction of aligned fibers
10 Silver, Mo in an epoxy matrix).
(metallic bonding) Cu,Ni
Steels
• often large atomic masses Tin, Zinc
Zirconia
Ceramics have... 5

ρ (g/cm3 )
Titanium
4 Al oxide
• less dense packing 3
Diamond
Si nitride
Aluminum Glass -soda Glass fibers
• often lighter elements Concrete
Silicon PTFE GFRE*
2
Polymers have... Magnesium Graphite
Silicone
Carbon fibers
CFRE*
Aramid fibers
PVC
• low packing density PET
PC
AFRE*
1
(often amorphous) HDPE, PS
PP, LDPE
• lighter elements (C,H,O)
0.5
Composites have... 0.4
Wood

• intermediate values 0.3

Data from Table B1, Callister 7e.

Chapter 3 – Structure of crystalline solids

 Section 3.6 – Polymorphism
• Two or more distinct crystal structures for the same
material (allotropy/polymorphism)
iron system
titanium: α, β-Ti
liquid
HCP α form at room temp.
BCC β form at 882 °C 1538ºC
BCC δ-Fe
carbon
1394ºC
diamond, graphite
FCC γ-Fe
The prevailing crystal 912ºC
structure depends on BCC α-Fe
temperature and
pressure.
Chapter 3 – Structure of crystalline solids
 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).

Chapter 3 – Structure of crystalline solids