1/23/2014

Energy and Packing

Non dense, random packing

Energy
typical neighbor
bond length

typical neighbor
bond energy

Dense, ordered packing

Energy
typical neighbor
bond length
r

typical neighbor
bond energy

Dense, ordered packed structures tend to have

lower energies.
Chapter 3 - 1

Materials and Packing

Crystalline materials...
atoms pack in periodic, 3D arrays
typical of: -metals
-many ceramics
-some polymers

crystalline SiO2
Adapted from Fig. 3.23(a),
Callister & Rethwisch 8e.

Noncrystalline materials...
atoms have no periodic packing
occurs for: -complex structures
-rapid cooling
"Amorphous" = Noncrystalline

Si

Oxygen

noncrystalline SiO2
Adapted from Fig. 3.23(b),
Callister & Rethwisch 8e.
Chapter 3 - 2

1/23/2014

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 - 3

Polycrystals

Chapter 3 - 4

1/23/2014

Crystal Structure

Chapter 3 - 5

Bravais Lattice

Chapter 3 -

1/23/2014

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)

Click once on image to start animation

(Courtesy P.M. Anderson)

Chapter 3 - 7

Body Centered Cubic Structure (BCC)

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

Chapter 3 - 8

1/23/2014

Face Centered Cubic Structure (FCC)

Chapter 3 - 9

FCC Stacking Sequence

ABCABC... Stacking Sequence
2D Projection
B
A sites
B sites

C
B

C
B

B
C
B

C sites

FCC Unit Cell

A
B
C

Chapter 3 - 10

1/23/2014

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(a),

Callister & Rethwisch 8e.
Chapter 3 - 11

Theoretical Density,
Density = =
=

where

Mass of Atoms in Unit Cell

Total Volume of Unit Cell

nA
VC NA

n = number of atoms/unit cell

A = atomic weight
VC = Volume of unit cell = a3 for cubic
NA = Avogadros number
= 6.022 x 1023 atoms/mol
Chapter 3 - 12

1/23/2014

Theoretical Density,
Ex: Cr (BCC)
A = 52.00 g/mol
R = 0.125 nm
n = 2 atoms/unit cell

R
atoms
unit cell

=
volume

a = 4R/ 3 = 0.2887 nm

Adapted from
Fig. 3.2(a), Callister &
Rethwisch 8e.

g
mol

2 52.00
a3 6.022 x 1023

unit cell

theoretical = 7.18 g/cm3

actual

= 7.19 g/cm3

atoms
mol

Chapter 3 - 13

Densities of Material Classes

In general
metals > ceramics > polymers
30
Why?
Metals have...

Ceramics have...
less dense packing
often lighter elements

Polymers have...

(g/cm3 )

close-packing
(metallic bonding)
often large atomic masses

low packing density

(often amorphous)
lighter elements (C,H,O)

Composites have...
intermediate values

Metals/
Alloys

20

Platinum
Gold, W
Tantalum

10

Silver, Mo
Cu,Ni
Steels
Tin, Zinc

5
4
3
2

0.5
0.4
0.3

Titanium
Aluminum
Magnesium

Graphite/
Ceramics/
Semicond

Composites/
fibers

Polymers

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

PTFE
Silicone
PVC
PET
PC
HDPE, PS
PP, LDPE

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

Wood

Data from Table B.1, Callister & Rethwisch, 8e.

Chapter 3 - 14

1/23/2014

Crystals as Building Blocks

Some engineering applications require single crystals:
-- diamond single
crystals for abrasives
(Courtesy Martin Deakins,
GE Superabrasives,
Worthington, OH. Used with
permission.)

-- turbine blades
Fig. 8.33(c), Callister &
Rethwisch 8e. (Fig. 8.33(c)
courtesy of Pratt and
Whitney).

Properties of crystalline materials

often related to crystal structure.
-- Ex: Quartz fractures more easily
along some crystal planes than
others.
(Courtesy P.M. Anderson)

Chapter 3 - 15

Polycrystals

Anisotropic

Most engineering materials are polycrystals.

Adapted from Fig. K,

color inset pages of
Callister 5e.
(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 grains are randomly oriented,

Isotropic

overall component properties are not directional.

Grain sizes typically range from 1 nm to 2 cm

(i.e., from a few to millions of atomic layers).

Chapter 3 - 16

1/23/2014

Single vs Polycrystals
Single Crystals

E (diagonal) = 273 GPa

Data from Table 3.3,
Callister & Rethwisch
8e. (Source of data is
R.W. Hertzberg,
Deformation and
Fracture Mechanics of
Engineering Materials,
3rd ed., John Wiley and
Sons, 1989.)

-Properties vary with

direction: anisotropic.
-Example: the modulus
of elasticity (E) in BCC iron:
E (edge) = 125 GPa

Polycrystals

200 m

-Properties may/may not

vary with direction.
-If grains are randomly
oriented: isotropic.
(Epoly iron = 210 GPa)

-If grains are textured,

anisotropic.

Adapted from Fig.

4.14(b), Callister &
Rethwisch 8e.
(Fig. 4.14(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 - 17

Polymorphism
Two or more distinct crystal structures for the same
material (allotropy/polymorphism)
iron system
titanium
liquid
, -Ti
1538C
-Fe
BCC
carbon
1394C
diamond, graphite
FCC
-Fe
912C
BCC

-Fe
Chapter 3 - 18

1/23/2014

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 & Rethwisch 8e.
Chapter 3 - 19

Point Coordinates
z

Point coordinates for unit cell

center are

111

a/2, b/2, c/2

000

a
x

Point coordinates for unit cell

corner are 111

2c

Translation: integer multiple of

lattice constants
identical
position in another unit cell

b
Chapter 3 - 20

10

1/23/2014

Crystallographic Directions
Algorithm

1. Vector repositioned (if necessary) to pass

through origin.
2. Read off projections in terms of
unit cell dimensions a, b, and c
3. Adjust to smallest integer values
4. Enclose in square brackets, no commas

[uvw]

ex: 1, 0, => 2, 0, 1 => [ 201 ]

-1, 1, 1 => [ 111 ]

where overbar represents a

negative index

families of directions <uvw>

Chapter 3 - 21

Linear Density
Linear Density of Atoms LD =

Number of atoms
Unit length of direction vector

[110]
ex: linear density of Al in [110]
direction
a = 0.405 nm

a
Adapted from
Fig. 3.1(a),
Callister &
Rethwisch 8e.

# atoms

LD =
length

= 3.5 nm1

2a

Chapter 3 - 22

11

1/23/2014

HCP Crystallographic Directions

z

Algorithm
1. Vector repositioned (if necessary) to pass
through origin.
2. Read off projections in terms of unit
cell dimensions a1, a2, a3, or c
3. Adjust to smallest integer values
4. Enclose in square brackets, no commas

a2

a3

[uvtw]

a2

a1
Adapted from Fig. 3.8(a),
Callister & Rethwisch 8e.

ex:

-a3

a2
2

, , -1, 0

=>

[ 1120 ]

a3

dashed red lines indicate

projections onto a1 and a2 axes

a1
2

a1
Chapter 3 - 23

HCP Crystallographic Directions

Hexagonal Crystals
4 parameter Miller-Bravais lattice coordinates are
related to the direction indices (i.e., u'v'w') as
follows.
z

[ u 'v 'w ' ] [ uvtw ]

1
(2 u ' - v ' )
3
1
v = (2 v ' - u ' )
3
t = - (u +v )

u=
a2

a3
a1

w = w'

Fig. 3.8(a), Callister & Rethwisch 8e.

Chapter 3 - 24

12

1/23/2014

Crystallographic Planes

Adapted from Fig. 3.10,

Callister & Rethwisch 8e.
Chapter 3 - 25

Crystallographic Planes
Miller Indices: Reciprocals of the (three) axial
intercepts for a plane, cleared of fractions &
common multiples. All parallel planes have
same Miller indices.
Algorithm
1. Read off intercepts of plane with axes in
terms of a, b, c
2. Take reciprocals of intercepts
3. Reduce to smallest integer values
4. Enclose in parentheses, no
commas i.e., (hkl)

Chapter 3 - 26

13

1/23/2014

Crystallographic Planes
z

example
1. Intercepts
2. Reciprocals
3.

Reduction

a
1
1/1
1
1

4.

Miller Indices

(110)

example
1. Intercepts
2. Reciprocals
3.

Reduction

a
1/2
1/
2
2

4.

Miller Indices

(100)

b
1
1/1
1
1

1/
0
0

x
b

1/
0
0

a
z

1/
0
0

c
y

a
x

Chapter 3 - 27

Crystallographic Planes
z
1.
2.

example
Intercepts
Reciprocals

3.

Reduction

4.

Miller Indices

a
1/2
1/
2
6

b
1
1/1
1
3

(634)

c
c
3/4
1/
4/3

4 a
x

Family of Planes {hkl}

Ex: {100} = (100), (010), (001), (100), (010), (001)
Chapter 3 - 28

14

1/23/2014

Crystallographic Planes (HCP)

In hexagonal unit cells the same idea is used
z

example
1. Intercepts
2. Reciprocals
3.

Reduction

a1
1
1
1
1

a2

1/
0
0

a3
-1
-1
-1
-1

c
1
1
1
1

a2

a3

4.

Miller-Bravais Indices

(1011)

a1
Adapted from Fig. 3.8(b),
Callister & Rethwisch 8e.

Chapter 3 - 29

Crystallographic Planes

We want to examine the atomic packing of

crystallographic planes
Iron foil can be used as a catalyst. The
atomic packing of the exposed planes is
important.
a) Draw (100) and (111) crystallographic planes
for Fe.
b) Calculate the planar density for each of these
planes.

Chapter 3 - 30

15

1/23/2014

Planar Density of (100) Iron

Solution: At T < 912C iron has the BCC structure.
2D repeat unit

(100)

Planar Density =
area
2D repeat unit

1
a2

4 3
3

4 3
R
3

Radius of iron R = 0.1241 nm

Adapted from Fig. 3.2(c), Callister & Rethwisch 8e.

atoms
2D repeat unit

a=

= 12.1

atoms
atoms
= 1.2 x 1019
2
nm
m2
Chapter 3 - 31

Planar Density of (111) Iron

Solution (cont): (111) plane

1 atom in plane/ unit surface cell

2a

atoms in plane
atoms above plane
atoms below plane

h=

3
a
2

4 3 16 3 2
area = 2 ah = 3 a = 3
R =
R
3
3

atoms
2D repeat unit

atoms =
= 7.0
2

Planar Density =
area
2D repeat unit

16 3
3

R2

nm

0.70 x 1019

atoms
m2

Chapter 3 - 32

16

1/23/2014

X-Ray Diffraction

Diffraction gratings must have spacings comparable to

the wavelength of diffracted radiation.
Cant resolve spacings <
Spacing is the distance between parallel planes of
atoms.
Chapter 3 - 33

X-Rays to Determine Crystal Structure

Incoming X-rays diffract from crystal planes.
reflections must
be in phase for
a detectable signal

extra
distance
travelled
by wave 2

Measurement of
critical angle, c,
allows computation of
planar spacing, d.

Adapted from Fig. 3.20,

Callister & Rethwisch 8e.

spacing
between
planes

X-ray
intensity
(from
detector)

d=

n
2 sin c

c
Chapter 3 - 34

17

1/23/2014

X-Ray Diffraction Pattern

z

Intensity (relative)

c
a
x

y (110)

a
x

(211)

(200)

Diffraction angle 2

Diffraction pattern for polycrystalline -iron (BCC)

Adapted from Fig. 3.22, Callister 8e.
Chapter 3 - 35

Octahedral and Tetrahedral Voids

Chapter 3 - 36

18

1/23/2014

Voids in FCC

Chapter 3 - 37

Octahedral Voids in HCP

Chapter 3 - 38

19

1/23/2014

Tetrahedral Voids in HCP

Chapter 3 - 39

Voids in BCC

Chapter 3 - 40

20

1/23/2014

Atomic Bonding in Ceramics

Degree of ionic character may be large or small:

CaF2: large
SiC: small

Adapted from Fig. 2.7, Callister & Rethwisch 8e. (Fig. 2.7 is adapted from Linus Pauling, The Nature of the
Chemical Bond, 3rd edition, Copyright 1939 and 1940, 3rd edition. Copyright 1960 by
Chapter 3 - 41
Cornell University.)

Factors that Determine Crystal Structure

1. Relative sizes of ions Formation of stable structures:
--maximize the # of oppositely charged ion neighbors.

unstable
stable
2. Maintenance of
Charge Neutrality :
--Net charge in ceramic
should be zero.
--Reflected in chemical
formula:
A X

CaF 2 :

Adapted from Fig. 12.1,

Callister & Rethwisch 8e.

+
-

stable
Ca 2+ +
cation

Fanions
F-

m p
m, p values to achieve charge neutrality
Chapter 3 - 42

21

1/23/2014

Coordination # and Ionic Radii

Centre of Triangle

Centre of Tetrahedron

Centre of Octahedron

Centre of Cube
Chapter 3 - 43

Rock Salt Structure

Same concepts can be applied to ionic solids in general.
Example: NaCl (rock salt) structure
rNa = 0.102 nm
rCl = 0.181 nm
rNa/rCl = 0.564
cations (Na+) prefer octahedral sites

Adapted from Fig. 12.2,

Callister & Rethwisch 8e.

Chapter 3 - 44

22

1/23/2014

AX Crystal Structures
Cesium Chloride structure:

rCs +
r

Cl

0.170
= 0.939
0.181

Since 0.732 < 0.939 < 1.0,

cubic sites preferred
Adapted from Fig. 12.3,
Callister & Rethwisch 8e.

So each Cs+ has 8 neighbor Cl-

Chapter 3 - 45

Zinc Blende Structure

rZn 0.074
=
= 0.402
rS 0.184

Tetrahedral sites

Chapter 3 - 46

23

1/23/2014

AmXp Crystal Structures

Fluorite structure

rCa +
rCl

0.100
= 0.752
0.133

Calcium Fluorite (CaF2)

Cations in cubic sites
UO2, ThO2, ZrO2, CeO2

Adapted from Fig. 12.5,

Callister & Rethwisch 8e.
Chapter 3 - 47

AmBnXp Crystal Structures

Perovskite structure
Ex: complex oxide
Barium Titanate- BaTiO3

Adapted from Fig. 12.6,

Callister & Rethwisch 8e.
Chapter 3 - 48

24