CRYSTAL STRUCTURES &

PROPERTIES

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- 1
 ENERGY AND PACKING
• Non dense, random packing Energy

typical neighbor
bond length

typical neighbor r
bond energy

• Dense, regular packing Energy

typical neighbor
bond length

typical neighbor r
bond energy

Dense, regular-packed structures tend to have

lower energy.
Chapter 3- 2
 MATERIALS AND PACKING
Crystalline materials...
• atoms pack in periodic, 3D arrays
• typical of: -metals
-many ceramics
-some polymers crystalline SiO2
Adapted from Fig. 3.18(a),
Callister 6e.

Si Oxygen
Noncrystalline materials...
• atoms have no periodic packing
• occurs for: -complex structures
-rapid cooling
"Amorphous" = Noncrystalline noncrystalline SiO2
Adapted from Fig. 3.18(b),
Callister 6e.

Chapter 3- 3
 METALLIC CRYSTALS
• tend to be densely packed.
• have several reasons for dense packing:
-Typically, only one element is present, so all atomic
radii are the same.
-Metallic bonding is not directional.
-Nearest neighbor distances tend to be small in
order to lower bond energy.

• have the simplest crystal structures.

We will look at three such structures...

Chapter 3- 4
SIMPLE CUBIC STRUCTURE (SC)
• Rare due to poor packing (only Po has this structure)
• Close-packed directions are cube edges.

• Coordination # = 6
(# nearest neighbors)

(Courtesy P.M. Anderson)

Chapter 3- 5
 ATOMIC PACKING FACTOR
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
a 4
unit cell 1 (0.5a) 3
3
R=0.5a APF =
a3 volume
close-packed directions
unit cell
contains 8 x 1/8 =
1 atom/unit cell
Adapted from Fig. 3.19,
Callister 6e. Chapter 3- 6
BODY CENTERED CUBIC STRUCTURE
(BCC)
• Close packed directions are cube diagonals.
--Note: All atoms are identical; the center atom is shaded
differently only for ease of viewing.

• Coordination # = 8

Adapted from Fig. 3.2,

Callister 6e.

(Courtesy P.M. Anderson) Chapter 3- 7

 ATOMIC PACKING FACTOR: BCC
• APF for a body-centered cubic structure = 0.68
Close-packed directions:
length = 4R
= 3a
Unit cell c ontains:
1 + 8 x 1/8
= 2 atoms/unit cell
R
Adapted from a
Fig. 3.2,
Callister 6e. atoms volume
4
unit cell 2 ( 3a/4 ) 3
3 atom
APF =
volume
a3
unit cell
Chapter 3- 8
FACE CENTERED CUBIC STRUCTURE
(FCC)
• Close packed directions are face diagonals.
--Note: All atoms are identical; the face-centered atoms are shaded
differently only for ease of viewing.

• Coordination # = 12

Adapted from Fig. 3.1(a),

Callister 6e.

(Courtesy P.M. Anderson)

Chapter 3- 9
 ATOMIC PACKING FACTOR: FCC
• APF for a body-centered cubic structure = 0.74
Close-packed directions:
length = 4R
= 2a
Unit cell c ontains:
6 x 1/2 + 8 x 1/8
= 4 atoms/unit cell
a
Adapted from
Fig. 3.1(a),
Callister 6e. atoms volume
4
unit cell 4 ( 2a/4 ) 3
3 atom
APF =
volume
a3
unit cell
Chapter 3- 10
 FCC STACKING SEQUENCE
• ABCABC... Stacking Sequence
• 2D Projection
A
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- 11
 HEXAGONAL CLOSE-PACKED
STRUCTURE (HCP)
• ABAB... Stacking Sequence
• 3D Projection • 2D Projection

A sites Top layer

B sites Middle layer

A sites Bottom layer

Adapted from Fig. 3.3,
Callister 6e.

• Coordination # = 12
• APF = 0.74

Chapter 3- 12
STRUCTURE OF COMPOUNDS: NaCl
• Compounds: Often have similar close-packed structures.
• Structure of NaCl • Close-packed directions
--along cube edges.

(Courtesy P.M. Anderson) (Courtesy P.M. Anderson)

Chapter 3- 13
 THEORETICAL DENSITY, 
# atoms/unit cell Atomic weight (g/mol)

 nA
Volume/unit cell Vc N A Avogadro's number
(cm 3 /unit cell) (6.023 x 10 23 atoms/mol)

Example: Copper
Data from Table inside front cover of Callister (see next slide):
• crystal structure = FCC: 4 atoms/unit cell
• atomic weight = 63.55 g/mol (1 amu = 1 g/mol)
• atomic radius R = 0.128 nm (1 nm = 10 cm) -7
Vc = a 3 ; For FCC, a = 4R/ 2 ; Vc = 4.75 x 10 -23 cm 3
Result: theoretical Cu = 8.89 g/cm 3
Compare to actual: Cu = 8.94 g/cm 3
Chapter 3- 14
 Characteristics of Selected Elements at 20C
At. Weight Density Crystal Atomic radius
Element Symbol (amu) (g/cm 3 ) Structure (nm)
Aluminum Al 26.98 2.71 FCC 0.143
Argon Ar 39.95 ------ ------ ------
Barium Ba 137.33 3.5 BCC 0.217
Beryllium Be 9.012 1.85 HCP 0.114
Boron B 10.81 2.34 Rhomb ------ Adapted from
Table, "Charac-
Bromine Br 79.90 ------ ------ ------ teristics of
Cadmium Cd 112.41 8.65 HCP 0.149 Selected
Elements",
Calcium Ca 40.08 1.55 FCC 0.197 inside front
Carbon C 12.011 2.25 Hex 0.071 cover,
Callister 6e.
Cesium Cs 132.91 1.87 BCC 0.265
Chlorine Cl 35.45 ------ ------ ------
Chromium Cr 52.00 7.19 BCC 0.125
Cobalt Co 58.93 8.9 HCP 0.125
Copper Cu 63.55 8.94 FCC 0.128
Flourine F 19.00 ------ ------ ------
Gallium Ga 69.72 5.90 Ortho. 0.122
Germanium Ge 72.59 5.32 Dia. cubic 0.122
Gold Au 196.97 19.32 FCC 0.144
Helium He 4.003 ------ ------ ------
Hydrogen H 1.008 ------ ------ ------ Chapter 3- 15
 DENSITIES OF MATERIAL CLASSES
Graphite/
metals ceramic s polymer s Metals/
Alloys
Ceramics/ Polymers
Composites/
fibers
Semicond
30
Why? Based on data in Table B1, Callister
Platinum
Metals have... 20 Gold, W
Tantalum
*GFRE, CFRE, & AFRE are Glass,
Carbon, & Aramid Fiber-Reinforced
• close-packing Epoxy composites (values based on
60% volume fraction of aligned fibers
(metallic bonding) 10 Silver, Mo
Cu,Ni
in an epoxy matrix).
Steels
• large atomic mass

 (g/cm 3 )
Tin, Zinc
Zirconia
Ceramics have... 5
Titanium
4 Al oxide
• less dense packing Diamond
Si nitride
3
(covalent bonding) Aluminum Glass -soda
Concrete
Glass fibers
Silicon PTFE
• often lighter elements 2 Magnesium G raphite
GFRE*
Carbon fibers
Silicone CFRE *
Polymers have... PVC
PET
Aramid fibers
AFRE *
• poor packing 1 PC
HDPE, PS
PP, LDPE
(often amorphous)
• lighter elements (C,H,O) 0.5 Wood
Composites have... 0.4
0.3
• intermediate values Data from Table B1, Callister 6e.
Chapter 3- 16
CRYSTALS AS BUILDING BLOCKS
• Some engineering applications require single crystals:
--diamond single --turbine blades
crystals for abrasives Fig. 8.30(c), Callister 6e.
(Fig. 8.30(c) courtesy
(Courtesy Martin Deakins, of Pratt and Whitney).
GE Superabrasives,
Worthington, OH. Used with
permission.)

• Crystal properties reveal features

of atomic structure.
--Ex: Certain crystal planes in quartz
fracture more easily than others.

(Courtesy P.M. Anderson)

Chapter 3- 17
 POLYCRYSTALS
• Most engineering materials are polycrystals.

Adapted from Fig. K, color

inset pages of Callister 6e.
(Fig. K is courtesy of Paul
E. Danielson, Teledyne
Wah Chang Albany)

1 mm

• Nb-Hf-W plate with an electron beam weld.

• Each "grain" is a single crystal.
• If crystals are randomly oriented,
overall component properties are not directional.
• Crystal sizes typ. range from 1 nm to 2 cm
(i.e., from a few to millions of atomic layers).
Chapter 3- 18
 SINGLE VS POLYCRYSTALS
• Single Crystals E (diagonal) = 273 GPa
Data from Table 3.3,
-Properties vary with Callister 6e.
(Source of data is R.W.
direction: anisotropic. Hertzberg, Deformation
and Fracture Mechanics of
-Example: the modulus Engineering Materials, 3rd
ed., John Wiley and Sons,
of elasticity (E) in BCC iron: 1989.)

E (edge) = 125 GPa

• Polycrystals
-Properties may/may not 200 m Adapted from Fig. 4.12(b),
Callister 6e.
vary with direction. (Fig. 4.12(b) is courtesy of
L.C. Smith and C. Brady,
-If grains are randomly the National Bureau of
Standards, Washington,
oriented: isotropic. DC [now the National
Institute of Standards and
(Epoly iron = 210 GPa) Technology, Gaithersburg,
-If grains are textured, MD].)

anisotropic.

Chapter 3- 19
X-RAYS TO CONFIRM CRYSTAL STRUCTURE
• Incoming X-rays diffract from crystal planes.
de
te c
to

”
r

“1
i n ra y
s
co s
X-
y reflections must
r- a
m
be in phase to
in

”
X

“2
g
detect signal

“1
g

”
extra
oi
n 
“2
distance tg Adapted from Fig. 3.2W,
 u 
”
travelled o Callister 6e.
by wave “2” spacing
d between
planes

• Measurement of: x-ray

Critical angles, c, intensity d=n /2sin c
(from
for X-rays provide
detector)
atomic spacing, d.

c
Chapter 3- 20
 SCANNING TUNNELING
MICROSCOPY
• Atoms can be arranged and imaged!
Photos produced from the
work of C.P. Lutz,
Zeppenfeld, and D.M.
Eigler. Reprinted with
permission from
International Business
Machines Corporation,
copyright 1995.

Carbon monoxide Iron atoms arranged on

molecules arranged on a a copper (111) surface.
platinum (111) surface. These Kanji characters
represent the word
“atom”.

Chapter 3- 21
 DEMO: HEATING AND
COOLING OF AN IRON WIRE
The same atoms can have
• Demonstrates "polymorphism" more than one crystal
structure.
Temperature, C
Liquid
1536
BCC Stable
1391
longer
heat up
FCC Stable
shorter!
914 longer!
BCC Stable
cool down
Tc 768 magnet falls off
shorter
Chapter 3- 22
 SUMMARY

• Atoms may assemble into crystalline or

amorphous 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).
• Material properties generally vary with single
crystal orientation (i.e., they are anisotropic),
but properties are generally non-directional
(i.e., they are isotropic) in polycrystals with
randomly oriented grains.

Chapter 3- 23
 ANNOUNCEMENTS
Reading:

Core Problems:

Self-help Problems:

Chapter 3- 0