Chapter 3: The Structure of Crystalline Solids

ISSUES TO EXPLORE...
• What is the difference in atomic arrangement
between crystalline and noncrystalline solids?
• What are the crystal structures of metals?
• What are the characteristics of crystal structures?
• How are crystallographic points, directions, and
planes specified?
• What characteristics of a material’s atomic
structure determine its density?

Chapter 3 - 1
 Energy and Packing
• Non dense, random packing Energy

typical neighbor
bond length

typical neighbor r
bond energy

• Dense, ordered packing Energy

typical neighbor
bond length

typical neighbor r
bond energy

Ordered structures tend to be nearer the

minimum in bonding energy and are more stable.
Chapter 3 - 2
 Materials and Atomic Arrangements
Si Oxygen
Noncrystalline materials...
• atoms have no periodic arrangement
• occurs for: -complex structures
-rapid cooling
"Amorphous" = Noncrystalline noncrystalline SiO2
Adapted from Fig. 3.24(b),
Callister & Rethwisch 10e.

Crystalline materials...
• atoms arranged in periodic, 3D arrays
• typical of: -metals
-many ceramics
-some polymers crystalline SiO2
Adapted from Fig. 3.24(a),
Callister & Rethwisch 10e.

Chapter 3 - 3
 Metallic Crystal Structures:
Atomic Packing
• Dense atomic packing for crystal structures
of metals
• Reasons for dense packing:
- Bonds between metal atoms are non-directional
- Nearest neighbor distances tend to be small in
order to lower bond energy
- High degree of shielding (of ion cores) provided
by free electron cloud
• Crystal structures for metals simpler than
structures for ceramics and polymers
We will examine four such structures for metals...
• Five characteristics -> Name, n, a(r), CN, APF Chapter 3 - 4
TopHat
Five Unit Cell Characteristics
• Name -> SC, BCC, FCC, HCP
• n -> # atoms in the unit cell
• a(r) -> unit cell edge length
• CN -> Coordination Number
– Number of nearest-neighbor or touching atoms
• APF -> Atomic Packing Factor
– Volume of atoms/Volume of unit cell
– (how much of cube volume is consumed by the
sphere(s))
Chapter 3 - 5
 Simple Cubic (SC) Crystal Structure
• Centers of atoms located at the eight corners of a cube
• Rare due to low packing density (only Po has this structure)
• Close-packed directions are cube edges.
ex: Po

1. Name
2. n
3. a(r)
4. CN
5. APF
Adapted from Fig. 3.3, Callister & Rethwisch 10e.

Chapter 3 - 6
 Simple Cubic (SC) Crystal Structure
• Centers of atoms located at the eight corners of a cube
• Rare due to low packing density (only Po has this structure)
• Close-packed directions are cube edges.
ex: Po • Coordination # =
(# nearest neighbors)

Adapted from Fig. 3.3, Callister & Rethwisch 10e.

Chapter 3 - 7
TopHat
Body-Centered Cubic Structure (BCC)
• Atoms located at __ cube corners with ___ at cube center
--Note: All atoms in the animation are identical; the center atom is shaded
differently for ease of viewing
ex: Cr, W, Fe (α), Ta, Mo
1. Name
2. n
3. a(r)
4. CN
5. APF
Adapted from Fig. 3.2, Callister & Rethwisch 10e.

Chapter 3 - 8
 Body-Centered Cubic Structure (BCC)
• Atoms located at 8 cube corners with a single atom at cube center
--Note: All atoms in the animation are identical; the center atom is shaded
differently for ease of viewing.
ex: Cr, W, Fe (α), Ta, Mo • Coordination # = 8

Adapted from Fig. 3.2, Callister & Rethwisch 10e.

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

Chapter 3 - 9
VMSE Screenshot – BCC Unit Cell

Chapter 3 - 10
TopHat
Face-Centered Cubic Structure (FCC)
• Atoms located at __ cube corners and at the centers of the ____
--Note: All atoms in the animation are identical; the face-centered atoms
are shaded differently for ease of viewing
ex: Al, Cu, Fe (γ), Au, Pb, Ni, Pt, Ag

1. Name
2. n
3. a(r)
4. CN
5. APF
Adapted from Fig. 3.1, Callister & Rethwisch 10e.

Chapter 3 - 11
 FCC Plane Stacking Sequence
• ABCABC... Stacking Sequence–Close-Packed Planes of Atoms
• 2D Projection
B B
C
A
A sites B B B
C C
B sites B B
C sites

A Close-Packed
• Stacking Sequence B
Referenced to an C Plane
FCC Unit Cell.

Chapter 3 - 12
 Hexagonal Close-Packed Structure
(HCP)
• ABAB... Stacking Sequence–Close-Packed Planes of Atoms
• 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
• Ideal c/a = 1.633
Chapter 3 - 13
 Theoretical Density for Metals, 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
= 6.022 x 1023 atoms/mol

Chapter 3 - 14
Theoretical Density Computation for Chromium

R
a

g
n A mol
ρ= = = ____ g/cm3
VC NA 6.022 x 1023 atoms
volume mol
unit cell ρactual = 7.15 g/cm3
Chapter 3 - 15
Theoretical Density Computation for Chromium

R
a

g
n A mol
ρ= = = ____ g/cm3
VC NA 6.022 x 1023 atoms
volume mol
unit cell ρactual = 7.15 g/cm3
Chapter 3 - 16
 Densities Comparison for Four Material Types
In general Metals/
Graphite/
Composites/
ρ metals > ρ ceramics > ρ polymers Alloys
Ceramics/
Semicond
Polymers
fibers
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
• often lighter elements 3
Diamond
Si nitride
Aluminum Glass -soda Glass fibers
Polymers have... 2
Concrete
Silicon PTFE GFRE*
Carbon fibers
• low packing density Magnesium Graphite
Silicone CFRE*
Aramid fibers
PVC AFRE*
(often amorphous) 1
PET
PS
• lighter elements (C,H,O) PE

Composites have... 0.5

• moderate to low densities 0.4
Wood

0.3

Chapter 3 - 17
 Single Crystals
• When the periodic arrangement of atoms (crystal structure)
extends without interruption throughout the entire specimen
-- diamond single -- single crystal for
crystals for abrasives turbine blade
(Courtesy Martin
Deakins, GE
Superabrasives,
Worthington, OH.
Used with
permission.)

-- Quartz single crystal

(Courtesy P.M. Anderson)

Fig. 8.35(c), Callister &

Rethwisch 10e.
(courtesy of Pratt and Whitney)
Chapter 3 - 18
 Polycrystalline Materials
• Most engineering materials are composed of many small,
single crystals (i.e., are polycrystalline)
large
grain
Courtesy of Paul E. Danielson, Teledyne Wah

1 mm
Chang Albany

small
grain
• Nb-Hf-W plate with an electron beam weld
• Each "grain" is a single crystal
• Grain sizes typically range from 1 nm to 2 cm
(i.e., from a few to millions of atomic layers)
Chapter 3 - 19
 Anisotropy

• Anisotropy — Property value depends on

crystallographic direction of measurement.
- Observed in single crystals. E (diagonal) = 273 GPa
- Example: modulus
of elasticity (E) in BCC iron

E(edge) ≠ E(diagonal)

E (edge) = 125 GPa

Unit cell of BCC iron

Chapter 3 - 20
 Isotropy
• Polycrystals
200 μm
- Properties may/may not
vary with direction
- If grains randomly oriented:
properties isotropic
(Epoly iron = 210 GPa)
- If grains textured (e.g.,
deformed grains have
preferential crystallographic
orientation):
Fig. 4.15(b), Callister & Rethwisch 10e.
properties anisotropic [Fig. 4.15(b) is courtesy of L.C. Smith and C. Brady, the
National Bureau of Standards, Washington, DC (now the
National Institute of Standards and Technology,
Gaithersburg, MD).]

Chapter 3 - 21
 Polymorphism/Allotropy
• Two or more distinct crystal structures for the same
material (allotropy/polymorphism)
Iron system
Titanium: α or β forms T
liquid
1538°
Carbon:

Temperature
C BCC
δ-Fe
diamond, graphite
1394°
C FCC
γ-Fe
912°C
α-Fe BCC

Chapter 3 - 22