CHAPTER 3: CRYSTAL

STRUCTURES & PROPERTIES

Why discuss crystal structure?
Density depends directly on atomic arrangement
Many properties depend on bond density and angle
(i.e. crystal orientation)
Crystal structure is basis for crystalline defects (Ch. 4)

K. M. Flores
Materials Science & Engineering

3-1

ENERGY AND PACKING

Non dense, random packing

Energy
typical neighbor
bond length

typical neighbor
bond energy

Dense, regular packing

Energy
typical neighbor
bond length

typical neighbor
bond energy

K. M. Flores
Materials Science & Engineering

3-2

MATERIALS AND PACKING

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.

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

K. M. Flores
Materials Science & Engineering

3-3

UNIT CELL
Small grouping of atoms that generate complete crystal
structure by repetitive displacement.
Edge of length a.
a

ATOMIC PACKING FACTOR

Relative density of atomic packing in unit cell, assuming
atoms are hard spheres.
APF =
K. M. Flores
Materials Science & Engineering

atoms volume
unit
cell atom
=
volume
unit cell
3-4

METALLIC CRYSTALS
Have the simplest crystal structures
Tend to be densely packed:
Metallic bonding is not directional.
Typically, only one element is present:
all atomic radii are the same.
Nearest neighbor distances typically small to
lower bond energy.

We will look at four such structures...

K. M. Flores
Materials Science & Engineering

3-5

SIMPLE CUBIC STRUCTURE (SC)

Rare due to poor packing (only Po has this structure)

K. M. Flores
Materials Science & Engineering

(Courtesy P.M. Anderson)

3-6

ATOMIC PACKING FACTOR for SC

APF = Volume of atoms in unit cell
Volume of unit cell

(4/3)r3
atoms volume
= unit cell atom
volume
unit cell
a3

Need: atoms/cell and r(a), relation between

atom radius and cube edge length:
Unit cell contains 1/8th of 8 atoms (corners)

atoms
unit cell

Adapted from Fig. 3.19,

Callister 6e.

volume

1
r

APF =

4
3

atom

(a/2)3

a3
SC: close-packed directions
K. M. Flores are cube edges
Materials Science & Engineering

volume
unit cell
3-7

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.

Adapted from Fig. 3.2,

Callister 6e.

K. M. Flores
Materials Science & Engineering

(Courtesy P.M. Anderson)

3-8

ATOMIC PACKING FACTOR for BCC

Close-packed direction are cube diagonals:

Unit cell contains:

1 (center) + 8 x 1/8 (corners)

r
Adapted from
Fig. 3.2,
Callister 6e.

a
atoms
unit cell

APF =

4
3
a3

volume

(a3/4)3

atom

volume
unit cell

K. M. Flores
Materials Science & Engineering

3-9

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.

Adapted from Fig. 3.1(a),

Callister 6e.

K. M. Flores
Materials Science & Engineering

(Courtesy P.M. Anderson)

3-10

ATOMIC PACKING FACTOR for FCC

Close-packed directions are face diagonals:

Unit cell contains of 6 atoms on face and

1/8th of 8 atoms on corners:

a
Adapted from
Fig. 3.1(a),
Callister 6e.

atoms

unit cell

APF =

(a2/4)3

volume
atom

volume

a3

unit cell

K. M. Flores
Materials Science & Engineering

3-11

FCC STACKING SEQUENCE

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

K. M. Flores
Materials Science & Engineering

A
B

B
C
B

B
C

B
C

B
A
B
C

3-12

HEXAGONAL CLOSE-PACKED
STRUCTURE (HCP)
ABAB... Stacking Sequence
Unit cell:

2D Projection
A sites

Top layer

B sites

Middle layer

A sites

Bottom layer

Adapted from Fig. 3.3,

Callister 6e.

K. M. Flores
Materials Science & Engineering

3-13

THEORETICAL DENSITY,
# atoms/unit cell

Volume/unit cell
(cm3/unit cell)

= nA
Vc N A

Atomic weight (g/mol)

Avogadro's number
(6.023 x 1023 atoms/mol)

Example: Copper
Data from Table inside front cover of Callister:
FCC crystal structure: n =
atomic weight: A =
atomic radius: r =
Vc = a3; For FCC, a = 4r/ 2 Vc =

Result: theoretical Cu =
actual Cu =
K. M. Flores
Materials Science & Engineering

3-14

DEMO: BCC FCC

TRANSFORMATION OF IRON
Demonstrates "polymorphism"
Temperature, C
1536

The same atoms can

have more than one
crystal structure.

Liquid
BCC Stable

1391
longer
heat up
FCC Stable

914

BCC Stable

Tc 768

cool down

shorter!
longer!
magnet falls off
shorter

K. M. Flores
Materials Science & Engineering

3-15

BCC FCC TRANSFORMATION OF

IRON AT 914C
Density will change because of change in crystal structure:
nA Fe
=
VcNA
Vc,BCC =

FCC nFCC A Fe
=
BCC Vc,FCCNA

Vc,BCCNA

n A
BCC Fe

nFCC Vc, BCC

=
nBCC Vc, FCC
Vc,FCC =

K. M. Flores
Materials Science & Engineering

3
aBCC

3
aFCC

3-16

STRUCTURE OF CERAMICS (Ch. 12)

Ionic compounds often have similar close-packed structures

Structure of NaCl
Cl- anions are red
Na+ cations are grey

Cl- and Na+ ions sit on

interpenetrating FCC lattices.
Close-packed directions
--along cube edges.
(Courtesy P.M. Anderson)

K. M. Flores
Materials Science & Engineering

3-17

STRUCTURE OF POLYMERS (Ch. 14)

Polymer = many mers
mer
H H H H H H
C C C C C C
H CH 3 H CH 3 H CH 3

mer
H H H H H H
C C C C C C
H H H H H H

mer
H H H H H H
C C C C C C
H Cl H Cl H Cl

Polyethylene (PE)

Polyvinyl chloride (PVC)

Polypropylene (PP)

Adapted from Fig. 14.2, Callister 6e.

Covalent chain configurations and strength:

secondary

bonding

Linear

Branched

Cross-Linked

Network

Direction of increasing strength

Typically amorphous: difficult to align chains in 3D

K. M. Flores
Materials Science & Engineering

3-18

DENSITIES OF MATERIAL CLASSES

metals > ceramics > polymers
Why?
Metals have...

Metals/
Alloys

Ceramics have...

Polymers have...

(g/cm 3)

30
20

Platinum
Gold, W
Tantalum

10

Silver, Mo
Cu,Ni
Steels
Tin, Zinc

5
4
3
2

Graphite/
Ceramics/
Semicond

Titanium
Aluminum
Magnesium

K. M. Flores
Materials Science & Engineering

0.5
0.4
0.3

Composites/
fibers

Based on data in Table B1, Callister

*GFRE, CFRE, & AFRE are Glass,
Carbon, & Aramid Fiber-reinforced
epoxy composites (values based on
60% volume fraction of aligned
fibers in an epoxy matrix).
Zirconia
Al oxide
Diamond
Si nitride
Glass -soda
Concrete
Silicon
Graphite

Composites have...

Polymers

PTFE
Silicone
PVC
PET
PC
HDPE, PS
PP, LDPE

Glass fibers
GFRE*
Carbon fibers
CFRE*
Aramid fibers
AFRE*

Wood
Data from Table B1, Callister 6e.

3-19

CRYSTALS AS BUILDING BLOCKS

Most engineering materials are polycrystalline
Adapted from Fig. K, color inset pages of
Callister 6e.
(Fig. K is courtesy of Paul E. Danielson,
Teledyne Wah Chang Albany)

grains = individual crystals

1 mm
Nb-Hf-W plate with an electron beam weld.

If crystals are randomly oriented,

overall component properties are not directional.

Crystal sizes typically range from 1 nm to 2 cm

(i.e., from a few to millions of atomic layers).
K. M. Flores
Materials Science & Engineering

3-20

10

CRYSTALS AS ENGINEERING
STRUCTURES
Some engineering applications require single crystals:
-- diamond single
crystals for abrasives

-- Ni superalloy turbine blades

for high performance engines
Fig. 8.30(c), Callister 6e.
(Fig. 8.30(c) courtesy
of Pratt and Whitney).

(Courtesy Martin Deakins,

GE Superabrasives,
Worthington, OH. Used with
permission.)

-- silicon wafer for

microelectronic devices
K. M. Flores
Materials Science & Engineering

Downloaded from
http://www.cstl.nist.gov/div837/Division/programs/microelect/microelect1.htm,
Sept. 7, 2005.

3-21

ISOTROPY vs. ANISOTROPY

Ediagonal

Single Crystals
- Anisotropy: properties vary
with direction
- Example: the modulus of
elasticity (E) in BCC iron:

Polycrystals

Data from Table 3.3, Callister 6e.

(Source of data is R.W. Hertzberg, Deformation
and Fracture Mechanics of Engineering
Materials, 3rd ed., John Wiley and Sons, 1989.)

Eedge

- Isotropy: properties same in

any direction
- Polycrystals are isotropic if
grains are randomly oriented
Epoly Fe =

200 m

Adapted from Fig. 4.12(b), Callister 6e.

(Fig. 4.12(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].)

- Polycrystals are anisotropic if

grains are textured
K. M. Flores
Materials Science & Engineering

3-22

11

X-RAYS TO CONFIRM CRYSTAL STRUCTURE

Incoming X-rays diffract off of crystal planes.

Measurement of:
Critical angles, c,
for X-rays provide
atomic spacing, d.

in
go
ut

1
g
in
m
co s
in -ray
X
extra
distance
traveled
by wave 2

de
te
ct
or
s
y
ra
X-

reflections must
be in phase to
detect signal
Adapted from Fig. 3.2W, Callister 6e.

spacing
d between
planes

x-ray
intensity
(from
detector)

d = n/(2 sinc)

K. M. Flores
Materials Science & Engineering

3-23

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
molecules arranged
on a platinum (111)
surface.

K. M. Flores
Materials Science & Engineering

Iron atoms arranged

on a copper (111)
surface. These Kanji
characters represent
the word atom.

3-24

12

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 structure (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.
K. M. Flores
Materials Science & Engineering

3-25

13