Chapter 3: The structure of crystalline solids

Outline
† Fundamental concepts
† Unit cells
† Metallic crystal structure
† Density and polymorphism
† Crystal systems

Fundamental concepts

• Crystalline materials: atoms

are situated in a repeating
or periodic array over large
atomic distances
• Crystalline structure: how
atoms, ions, or molecules
are arranged spatially (c)

• Lattice: a three-dimensional
array of points coinciding
with atom position

Fig 3.1 (a) a hard sphere unit cell

(b) a reduced-sphere unit cell, (c) an
aggregate of many atoms

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 Unit cells

• Small repeating units in a

crystal
• Basic structural unit or
building block of the crystal
structure
• Not unique
• A highest level of geometrical
symmetry

Simple cubic structure (SC)

• Close-packed directions are cube edges.

• Atoms per unit cell = 8 x 1/8 =1
• Coordination # (nearest neighbors) = 6
• Rare due to low packing density (only Po has this structure)

(Courtesy P.M. Anderson)

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 Atomic packing factor (APF)

Volume of atoms in unit cell*

APF =
Volume of unit cell
*assume hard spheres
• APF for a simple cubic structure = 0.52
volume
atoms atom
4
a unit cell 1 π (0.5a) 3
3
R=0.5a APF =
a3 volume
close-packed directions unit cell

Adapted from Fig. 3.23,

Callister 7e.

Metallic crystal structure

ο Features of metallic crystal structure

• non-directional in nature
• no restriction on the number and
position of nearest-neighbor atoms
• close-packed: low energy
• common type: face-centered cubic
(FCC), body-centered cubic (BCC),
hexagonal closed-packed (HCP)

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 The FCC crystal structure

ο Total atoms per unit cell=4

• 8x1/8 atoms at corner+6x1/2
face-centered atoms=4
ο The relation between cubic
edge a and the radius R
a = 2 2R
ο Coordination number=12
• the number of nearest-
neighbor or touching atoms
ο Atomic packing factor (APF)
• APF=0.74

Atomic packing factor: FCC

• APF for a face-centered cubic structure = 0.74

maximum achievable APF
Close-packed directions:
length = 4R = 2 a
2a
Unit cell contains:
6 x 1/2 + 8 x 1/8
= 4 atoms/unit cell
a
Adapted from
Fig. 3.1(a),
Callister 7e. atoms volume
4
unit cell 4 π ( 2a/4) 3
3 atom
APF =
volume
a3
unit cell

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 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

The BCC crystal structure

• Total atoms per unit cell

8x1/8 atoms at corner+1 body-centered atoms=2
• Coordination number=8

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 Atomic packing factor: BCC

• APF for a body-centered cubic structure = 0.68

3a

2a

Close-packed directions:
R length = 4R = 3 a
Adapted from
Fig. 3.2(a), Callister 7e.
a
atoms volume
4
unit cell 2 π ( 3a/4) 3
3 atom
APF =
volume
a3
unit cell

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 Adapted from Fig. 3.3(a),
Callister 7e.

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

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 Theoretical density and polymorphism

• Density computation
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
• Polymorphism: a phenomenon that material has more than
one crystal structure

Theoretical density (example)

ο Ex: Cr (BCC)
ο A = 52.00 g/mol
ο R = 0.125 nm
ο 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

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 Densities of material classes

In general Graphite/
ρmetals > ρceramics > ρpolymers
Metals/ Composites/
Ceramics/ Polymers
Alloys fibers
Semicond
30
Why? Platinum
Based on data in Table B1, Callister
*GFRE, CFRE, & AFRE are Glass,
20 Gold, W
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

ρ (g/cm3 )
5
Ceramics have... 4
Titanium
Al oxide
Diamond
• less dense packing 3 Si nitride
Aluminum Glass -soda Glass fibers
• often lighter elements Concrete
Silicon PTFE GFRE*
2 Carbon fibers
Polymers have... Magnesium Graphite
Silicone 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.

Crystal systems

• 7 crystal systems

• 14 crystal lattices

a, b, and c are the lattice constants

Fig. 3.4, Callister 7e.

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Crystal systems

Crystal systems

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 Crystal Systems

Hexagonal:
Cubic: Tetragonal:
Emerald
Lead ore Rhombic: idocrase
Topaz

Monoclinic: Triclinic:
Gypsum Axinite

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