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

Dense, ordered packed structures tend to have

lower energies.
1

Materials and Packing

Crystalline materials...
atoms pack in periodic, 3D arrays
typical of: -metals
-many ceramics
-some polymers crystalline SiO2
Adapted from Fig. 3.40(a),
Callister & Rethwisch 3e.

Si Oxygen
Noncrystalline materials...
atoms have no periodic packing
occurs for: -complex structures
-rapid cooling
"Amorphous" = Noncrystalline noncrystalline SiO2
Adapted from Fig. 3.40(b),
Callister & Rethwisch 3e.

Metallic Crystal Structures

How can we stack metal atoms to minimize
empty space?
2-dimensions

vs.

3
 Metallic Crystal Structures
Tend to be densely packed.
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.
- Electron cloud shields cores from each other
Have the simplest crystal structures.

We will examine three such structures...

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)

(Courtesy P.M. Anderson)

5

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
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. 3.42,
Callister & Rethwisch 3e. 6
 Body Centered Cubic Structure (BCC)
Atoms touch each other along cube diagonals.
--Note: All atoms are identical; the center atom is shaded
differently only for ease of viewing.

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

Coordination # = 8

Adapted from Fig. 3.2,

Callister & Rethwisch 3e.

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

(Courtesy P.M. Anderson)
7

Atomic Packing Factor: BCC

APF for a body-centered cubic structure = 0.68
3a

2a

Close-packed directions:
Adapted from R length = 4R = 3 a
Fig. 3.2(a), Callister &
Rethwisch 3e.
a
atoms volume
4
unit cell 2 ( 3a/4) 3
3 atom
APF =
volume
a3
unit cell 8

Face Centered Cubic Structure (FCC)

Atoms touch each other along face diagonals.
--Note: All atoms are identical; the face-centered atoms are shaded
differently only for ease of viewing.

ex: Al, Cu, Au, Pb, Ni, Pt, Ag

Coordination # = 12

QuickTime and a
Cinepak decompressor
are needed to see this picture.

Adapted from Fig. 3.1, Callister & Rethwisch 3e.

4 atoms/unit cell: 6 face x 1/2 + 8 corners x 1/8

(Courtesy P.M. Anderson)
9
 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 & atoms volume
Rethwisch 3e. 4
unit cell 4 ( 2a/4) 3
3 atom
APF =
volume
a3
unit cell
10

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

11

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 & Rethwisch 3e.

Coordination # = 12 6 atoms/unit cell

APF = 0.74 ex: Cd, Mg, Ti, Zn
c/a = 1.633 12
 Theoretical Density, 

Mass of Atoms in Unit Cell

Density =  =
Total Volume of Unit Cell

nA
=
VC NA

where 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

13

Theoretical Density,
Ex: Cr (BCC)
A = 52.00 g/mol
R = 0.125 nm
n = 2 atoms/unit cell
R
Adapted from a a = 4R/ 3 = 0.2887 nm
Fig. 3.2(a), Callister &
Rethwisch 3e.
atoms
g
unit cell 2 52.00 = 7.18 g/cm3
mol theoretical
= = 7.19 g/cm3
a 3 6.022 x 1023 actual

volume atoms
unit cell mol 14

Atomic Bonding in Ceramics

Bonding:
-- Can be ionic and/or covalent in character.
-- % ionic character increases with difference in
electronegativity of atoms.
Degree of ionic character may be large or small:
CaF2: large
SiC: small

Adapted from Fig. 2.7, Callister & Rethwisch 3e. (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
Cornell University. 15
 Ceramic Crystal Structures
Oxide structures
oxygen anions larger than metal cations
close packed oxygen in a lattice (usually FCC)
cations fit into interstitial sites among oxygen ions

16

Factors that Determine Crystal Structure

1. Relative sizes of ions Formation of stable structures:
--maximize the # of oppositely charged ion neighbors.
- - - - - -
+ + +
Adapted from Fig. 3.4,
Callister & Rethwisch 3e.
- - - - - -
unstable stable stable
2. Maintenance of
Charge Neutrality : F-
CaF 2 : Ca 2+ +
--Net charge in ceramic
cation anions
should be zero.
--Reflected in chemical F-
formula:
A m Xp
m, p values to achieve charge neutrality
17

Coordination # and Ionic Radii

r cation
Coordination # increases with r
anion
To form a stable structure, how many anions can
surround around a cation?
r cation Coord ZnS
r anion # (zinc blende)
Adapted from Fig. 3.7,
< 0.155 2 linear Callister & Rethwisch 3e.

0.155 - 0.225 3 triangular NaCl

(sodium
0.225 - 0.414 4 tetrahedral chloride)
Adapted from Fig. 3.5,
Callister & Rethwisch 3e.

0.414 - 0.732 6 octahedral CsCl

(cesium
chloride)
0.732 - 1.0 8 cubic Adapted from Fig. 3.6,
Adapted from Table 3.3, Callister & Rethwisch 3e.
Callister & Rethwisch 3e.
18
 Computation of Minimum Cation-Anion
Radius Ratio
Determine minimum rcation/ranion for an octahedral site
(C.N. = 6)
2ranion  2rcation
2a

a
2ranion

2r anion2r cation=2  2 r anion

r anionr cation=  2r anion r cation=  21 r anion

r cation
= 21=0 . 414
r anion
29/09/10 19

Example Problem: Predicting the Crystal

Structure of FeO
On the basis of ionic radii, what crystal structure
would you predict for FeO?
Cation Ionic radius (nm) Answer:
Al 3+ 0.053 rca ti o n 0.077


Fe 2+ 0.077 ra n i o n 0.140
Fe 3+ 0.069
0. 550
Ca 2+ 0.100
based on this ratio,
-- coord # = 6 because
Anion
0.414 < 0.550 < 0.732
O2- 0.140
-- crystal structure is NaCl
Cl - 0.181
Data from Table 3.4,
F- 0.133 Callister & Rethwisch 3e.
20

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. 3.5,

Callister & Rethwisch 3e.

21
 MgO and FeO
MgO and FeO also have the NaCl structure

O2- rO = 0.140 nm

Mg2+ rMg = 0.072 nm

rMg/rO = 0.514

cations prefer octahedral sites

Adapted from Fig. 3.5,

Callister & Rethwisch 3e.

So each Mg2+ (or Fe2+) has 6 neighbor oxygen atoms

22

AX Crystal Structures
AXType Crystal Structures include NaCl, CsCl, and zinc blende

Cesium Chloride structure:

Cs 0.170


0. 939
0. 181
Cl

 Since 0.732 < 0.939 < 1.0,

cubic sites preferred

Adapted from Fig. 3.6, So each Cs+ has 8 neighbor Cl-
Callister & Rethwisch 3e.

23

AX2 Crystal Structures

Fluorite structure

Calcium Fluorite (CaF2)

Cations in cubic sites

UO2, ThO2, ZrO2, CeO2

Antifluorite structure
positions of cations and
anions reversed
Adapted from Fig. 3.8,
Callister & Rethwisch 3e.

24
 Density Computations for Ceramics

Number of formula units/unit cell

'
n  A C  A A 

=
VCNA
Avogadros number
Volume of unit cell

AC= sum of atomic weights of all cations in formula unit

AA= sum of atomic weights of all anions in formula unit

29/09/10 25

Densities of Material Classes

In general Metals/
Graphite/
Composites/
metals > ceramics > 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
 (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 HDPE, PS
(often amorphous) PP, LDPE
lighter elements (C,H,O)
0.5
Composites have... 0.4
Wood

intermediate values 0.3

Data from Table B.1, Callister & Rethwisch, 3e.
26

Glass Structure
Basic Unit: Glass is noncrystalline (amorphous)
4- Fused silica is SiO2 to which no
Si0 4 tetrahedron
impurities have been added
Si 4+ Other common glasses contain
O 2- impurity ions such as Na+, Ca2+,
Al3+, and B3+

Quartz is crystalline
Na +
SiO2: Si 4+
O 2-

(soda glass)
Adapted from Fig. 3.41,
Callister & Rethwisch 3e.

29
 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.)
Properties of crystalline materials
often related to crystal structure.
-- Ex: Quartz fractures more easily
along some crystal planes than
others.
Polycrystals
Most engineering materials are polycrystals.
1 mm
Nb-Hf-W plate with an electron beam weld.
Each "grain" is a single crystal.
If grains are randomly oriented,
overall component properties are not directional.
Grain sizes typ. range from 1 nm to 2 cm
(i.e., from a few to millions of atomic layers).
Single vs Polycrystals
Single Crystals
-Properties vary with
direction: anisotropic.
-Example: the modulus
of elasticity (E) in BCC iron:
Polycrystals
-Properties may/may not
vary with direction.
-If grains are randomly
oriented: isotropic.
(Epoly iron = 210 GPa)
-If grains are textured,
anisotropic.
-- turbine blades
Fig. 9.40(c), Callister &
Rethwisch 3e. (Fig. 9.40(c)
courtesy of Pratt and
Whitney).
(Courtesy P.M. Anderson)
28
Anisotropic
Adapted from Fig. K,
color inset pages of
Callister 5e.
(Fig. K is courtesy of
Paul E. Danielson,
Teledyne Wah Chang
Albany)
Isotropic
29
E (diagonal) = 273 GPa
Data from Table 3.7,
Callister & Rethwisch
3e. (Source of data is
R.W. Hertzberg,
Deformation and
Fracture Mechanics of
Engineering Materials,
3rd ed., John Wiley and
Sons, 1989.)
E (edge) = 125 GPa
200 m Adapted from Fig.
5.19(b), Callister &
Rethwisch 3e.
(Fig. 5.19(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].)
30
 Polymorphism
Two or more distinct crystal structures for the same
material (allotropy/polymorphism)
iron system
titanium
liquid
, -Ti
1538C
BCC
-Fe
carbon
diamond, graphite 1394C
FCC -Fe
912C
BCC -Fe

31

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. 3.20, Callister & Rethwisch 3e.

32

Point Coordinates
z
111 Point coordinates for unit cell
c center are
a/2, b/2, c/2

000
y
a b
Point coordinates for unit cell
x corner are 111
z 2c

Translation: integer multiple of

lattice constants identical
b y position in another unit cell
b
33
 Crystallographic Directions
z Algorithm
1. Vector repositioned (if necessary) to pass
through origin.
2. Read off projections in terms of
unit cell dimensions a, b, and c
y 3. Adjust to smallest integer values
4. Enclose in square brackets, no commas

x [uvw]

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

-1, 1, 1 => [ 111 ] where overbar represents a
negative index
families of directions <uvw>
34

Linear Density
Number of atoms
Linear Density of Atoms
LD =
Unit length of direction vector

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

# atoms
a 2
LD

3.5 nm  1
length 2a

35

HCP Crystallographic Directions

z
Algorithm
1. Vector repositioned (if necessary) to pass

through origin.
a2 2. Read off projections in terms of unit
cell dimensions a1, a2, a3, or c
- 3. Adjust to smallest integer values
a3
4. Enclose in square brackets, no commas
a2
a1 [uvtw]
Adapted from Fig. 3.24(a),
Callister & Rethwisch 3e.
a2 -a3
2

ex: , , -1, 0 => [ 1120 ] a3

a1
2
dashed red lines indicate
projections onto a1 and a2 axes a1
36
 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
u
(2 u ' - v ')
3
a2
1
v
( 2 v ' - u ')
- 3
a3
t
- ( u +v )
a1
w
w'
Fig. 3.24(a), Callister & Rethwisch 3e.

37

Crystallographic Planes

Adapted from Fig. 3.25,

Callister & Rethwisch 3e.
38

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)

39
 Crystallographic Planes
z
example a b c
1. Intercepts 1 1  c
2. Reciprocals 1/1 1/1 1/
1 1 0
3. Reduction 1 1 0 y
a b
4. Miller Indices (110)
x
z
example a b c
1. Intercepts 1/2   c
2. Reciprocals 1/ 1/ 1/
2 0 0
3. Reduction 2 0 0
y
4. Miller Indices (100) a b
x
40

Crystallographic Planes
z
example a b c c
1. Intercepts 1/2 1 3/4
2. Reciprocals 1/ 1/1 1/
2 1 4/3 y
3. Reduction 6 3 4 a b

4. Miller Indices (634) x

Family of Planes {hkl}

Ex: {100} = (100), (010), (001), (100), (010), (001)

41

Crystallographic Planes (HCP)

In hexagonal unit cells the same idea is used
z

example a1 a2 a3 c
1. Intercepts 1  -1 1
2. Reciprocals 1 1/ -1 1
1 0 -1 1 a2

3. Reduction 1 0 -1 1
a3

4. Miller-Bravais Indices (1011) a1

Adapted from Fig. 3.24(b),

Callister & Rethwisch 3e.

42
 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.

43

Planar Density of (100) Iron

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

(100) 4 3
a
R
3

Adapted from Fig. 3.2(c), Callister & Rethwisch 3e. Radius of iron R = 0.1241 nm
atoms
2D repeat unit 1
1 atoms atoms
Planar Density = = 2 = 12.1 = 1.2 x 1019
area a2 4 3 nm2 m2
R
2D repeat unit 3
44

Planar Density of (111) Iron

Solution (cont): (111) plane 1 atom in plane/ unit surface cell

2a atoms in plane
atoms above plane
nit

atoms below plane

tu
ea
ep

3
h

r

a
2D

2
2
4 3 16 3 2
area
2 ah
3 a 2
3 R
R
atoms
3 3
2D repeat unit 1
atoms atoms
Planar Density = = 7.0 = 0.70 x 1019
2
area 16 3 2
nm m2
R
2D repeat unit 3
45
 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.
46

X-Rays to Determine Crystal Structure

Incoming X-rays diffract from crystal
d planes. et
ec
t or

1
in -ray
co s

ys
X

reflections must
m

ra be in phase for
in

X-
2
g
1

a detectable signal

ng 
extra
oi
2

distance tg Adapted from Fig. 3.37,

travelled ou Callister & Rethwisch 3e.

by wave 2 spacing
d between
planes

Measurement of X-ray
intensity n
critical angle, c, d

(from 2 sin c
allows computation of
detector)
planar spacing, d.

c
47

X-Ray Diffraction Pattern

z z z
c c c

y (110) y y
a b a b a b
Intensity (relative)

x x x (211)

(200)

Diffraction angle 2

Diffraction pattern for polycrystalline -iron (BCC)

Adapted from Fig. 3.20, Callister 5e.

48