Chapter 4: The Structure of Crystalline Solids

ISSUES TO ADDRESS...
What are common crystal structures for
metals and ceramics?
What features of a metals/ceramics atomic
structure determine its density?
How do the crystal structures of ceramic
materials differ from those for metals?

Chapter 4 - 1

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 4 - 2

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.

Metals have the simplest crystal structures.

We will examine three such structures...

Chapter 4 - 3

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)

Fig. 4.2, Callister & Rethwisch 9e.

Chapter 4 - 4

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
atoms
unit cell

a
R = 0.5a
close-packed directions
contains 8 x 1/8 =
1 atom/unit cell
Adapted from Fig. 4.2 (a),
Callister & Rethwisch 9e.

APF =

volume
atom
4
(0.5a) 3
1
3
a3

volume
unit cell

Chapter 4 - 5

1. 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. 4.1,

Callister & Rethwisch 9e.

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

Chapter 4 - 6

Atomic Packing Factor: BCC

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

a
2a
Adapted from
Fig. 4.1(a), Callister &
Rethwisch 9e.

Close-packed directions:
length = 4R = 3 a

atoms
volume
4
( 3a/4 ) 3
2
unit cell
atom
3
APF =
volume
a3
unit cell

Chapter 4 - 7

2. 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

Adapted from Fig. 3.1, Callister & Rethwisch

9e.

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

Chapter 4 - 8

Atomic Packing Factor: FCC

APF for a face-centered cubic structure = 0.74
maximum achievable APF

2a

Adapted from
Fig. 3.1(a),
Callister &
Rethwisch 9e.

Close-packed directions:
length = 4R = 2 a
Unit cell contains:
6 x 1/2 + 8 x 1/8
= 4 atoms/unit cell
atoms
volume
4
3
( 2a/4 )
4
unit cell
atom
3
APF =
volume
3
a
unit cell
Chapter 4 - 9

FCC Stacking Sequence

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

A
B
C

Chapter 4 - 10

3. 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. 4.3(a),

Callister & Rethwisch 9e.

Coordination # = 12
APF = 0.74

6 atoms/unit cell
ex: Cd, Mg, Ti, Zn

c/a = 1.633
Chapter 4 - 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 4 - 12

Theoretical Density,
Ex: Cr (BCC)
A = 52.00 g/mol
R = 0.125 nm
n = 2 atoms/unit cell
Adapted from
Fig. 4.1(a), Callister &
Rethwisch 9e.

atoms
unit cell
=

volume
unit cell

a
2 52.00

a 3 6.022 x 1023

a = 4R/ 3 = 0.2887 nm
g
mol

theoretical

= 7.18 g/cm3

actual

= 7.19 g/cm3

atoms
mol
Chapter 4 - 13

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

Chapter 4 - 14

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

Chapter 4 - 15

Factors that Determine Crystal Structure

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

unstable
2. Maintenance of
Charge Neutrality :

stable

--Net charge in ceramic

should be zero.
--Reflected in chemical
formula:

CaF 2 :

Adapted from Fig. 4.4,

Callister & Rethwisch 9e.

stable
Ca 2+ +
cation

Fanions
F-

A m Xp
m, p values to achieve
charge neutrality

Chapter 4 - 16

Coordination Number and Ionic Radii

r cation
Coordination Number increases with r
anion

To form a stable structure, how many anions can

surround around a cation?
r cation
r anion
< 0.155

Coord.
Number
2
linear

0.155 - 0.225

0.225 - 0.414

4 tetrahedral

0.414 - 0.732

6 octahedral

0.732 - 1.0

Adapted from Table 4.3,

Callister & Rethwisch 9e.

triangular

cubic

ZnS
(zinc blende)
Adapted from Fig. 4.7,
Callister & Rethwisch 9e.

NaCl
(sodium
chloride)

Adapted from Fig. 4.5,

Callister & Rethwisch 9e.

CsCl
(cesium
chloride)
Adapted from Fig. 4.6,
Callister & Rethwisch 9e.
Chapter 4 - 17

Bond Hybridization
Bond Hybridization is possible when there is significant
covalent bonding
hybrid electron orbitals form
For example for SiC

XSi = 1.8 and XC = 2.5

~ 89% covalent bonding

Both Si and C prefer sp3 hybridization
Therefore, for SiC, Si atoms occupy tetrahedral sites

Chapter 4 - 18

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)
Al 3+
0.053
Fe 2+
0.077
Fe 3+
0.069
Ca 2+
0.100
Anion
O2Cl F-

0.140
0.181
0.133

Answer:

rcation 0.077

ranion 0.140
0.550
based on this ratio,
-- coord # = 6 because
0.414 < 0.550 < 0.732
-- crystal structure is NaCl

Data from Table 4.4,

Callister & Rethwisch 9e.
Chapter 4 - 19

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. 4.5,

Callister & Rethwisch 9e.

Chapter 4 - 20

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. 4.5,
Callister & Rethwisch 9e.

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

Chapter 4 - 21

AX Crystal Structures
AXType Crystal Structures include NaCl, CsCl, and zinc blende
Cesium Chloride structure:

Since 0.732 < 0.939 < 1.0,

Fig. 4.6, Callister & Rethwisch 9e.

cubic sites preferred

So each Cs+ has 8 neighbor Cl-

Chapter 4 - 22

AX2 Crystal Structures

Fluorite structure
Calcium Fluorite (CaF2)
Cations in cubic sites
UO2, ThO2, ZrO2, CeO2
Antifluorite structure
positions of cations and
anions reversed
Fig. 4.8, Callister & Rethwisch 9e.

Chapter 4 - 23

ABX3 Crystal Structures

Perovskite structure
Ex: complex oxide
BaTiO3

Fig. 4.9, Callister &

Rethwisch 9e.

Chapter 4 - 24

Density Computations for Ceramics

Number of formula units/unit cell

Avogadros number
Volume of unit cell
= sum of atomic weights of all cations in formula unit
= sum of atomic weights of all anions in formula unit

Chapter 4 - 25

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
1

0.5
0.4
0.3

Titanium
Aluminum
Magnesium

Graphite/
Ceramics/
Semicond

Polymers

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

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, 9e.
Chapter 4 - 26

Silicate Ceramics
Most common elements on earth are Si & O

Si4+
O2Figs. 4.10 & 4.11, Callister & Rethwisch
9e

crystobalite

SiO2 (silica) polymorphic forms are quartz,

crystobalite, & tridymite
The strong Si-O bonds lead to a high melting
temperature (1710C) for this material
Chapter 4 - 27

Silicates
Bonding of adjacent SiO44- accomplished by the sharing
of common corners, edges, or faces

Mg2SiO4

Ca2MgSi2O7

Adapted from Fig.

4.13, Callister &
Rethwisch 9e.

Presence of cations such as Ca2+, Mg2+, & Al3+

1. maintain charge neutrality, and
2. ionically bond SiO44- to one another
Chapter 4 - 28

Glass Structure
Basic Unit:
4Si0 4 tetrahedron
Si 4+
O2-

Quartz is crystalline
SiO2:

Glass is noncrystalline (amorphous)

Fused silica is SiO2 to which no
impurities have been added
Other common glasses contain
impurity ions such as Na+, Ca2+,
Al3+, and B3+
Na +
Si 4+
O2-

(soda glass)
Adapted from Fig. 4.12,
Callister & Rethwisch 9e.
Chapter 4 - 29

Layered Silicates

Layered silicates (e.g., clays, mica,

talc)
SiO4 tetrahedra connected
together to form 2-D plane

A net negative charge is associated

with each (Si2O5)2- unit
Negative charge balanced by
adjacent plane rich in positively
charged cations

Fig. 4.14, Callister &

Rethwisch 9e.

Chapter 4 - 30

Layered Silicates (cont)

Kaolinite clay alternates (Si2O5)2- layer with Al2(OH)42+
layer

Fig. 4.15, Callister &

Rethwisch 9e.

Note: Adjacent sheets of this type are loosely bound to

one another by van der Waals forces.
Chapter 4 - 31

Polymorphic Forms of Carbon

Diamond
tetrahedral bonding of
carbon
hardest material known
very high thermal
conductivity

large single crystals gem

stones
small crystals used to
grind/cut other materials
diamond thin films
hard surface coatings used
for cutting tools, medical
devices, etc.

Fig. 4.17, Callister &

Rethwisch 9e.

Chapter 4 - 32

Polymorphic Forms of Carbon (cont)

Graphite
layered structure parallel hexagonal arrays of
carbon atoms

Fig. 4.18, Callister &

Rethwisch 9e.

weak van der Waals forces between layers

planes slide easily over one another -- good lubricant
Chapter 4 - 33

Crystallinity in Polymers

Fig. 4.19, Callister &

Rethwisch 9e.

Ordered atomic
arrangements involving
molecular chains
Crystal structures in terms
of unit cells
Example shown
polyethylene unit cell

Chapter 4 - 34

Crystals as Building Blocks

Some engineering applications require single crystals:
-- diamond single
crystals for abrasives

-- turbine blades

(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.

(Courtesy P.M. Anderson)

Chapter 4 - 35

Polycrystals
Most engineering materials are polycrystals.

Anisotropic

Fig. K, color inset pages

of Callister 5e.
(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 4 - 36

Single vs Polycrystals
Single Crystals

E (diagonal) = 273 GPa

Data from Table 3.3,
Callister & Rethwisch 9e.

-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)

(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.

6.19(b), Callister &
Rethwisch 9e.
[Fig. 6.19(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).]

-If grains are textured,

anisotropic.
Chapter 4 - 37

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
-Fe
FCC
912C
BCC

-Fe

Chapter 4 - 38

Linear Density
Linear Density of Atoms LD =

[110]

a
Adapted from
Fig. 3.1(a),
Callister &
Rethwisch 9e.

Number of atoms
Unit length of direction vector

ex: linear density of Al in [110]

direction
a = 0.405 nm

# atoms

LD
length

2
2a

3.5 nm1

Chapter 4 - 39

Planar Density of (100) Iron

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

(100)

4 3
R
3

Fig. 4.2(c), Callister & Rethwisch 9e [from W. G. Moffatt, G. W.

Pearsall, and J. Wulff, The Structure and Properties of Materials, Vol. I,
Structure, p. 51. Copyright 1964 by John Wiley & Sons, New York.
Reprinted by permission of John Wiley & Sons, Inc.]

atoms
2D repeat unit

Planar Density =
area
2D repeat unit

1
a2

1
4 3
3

Radius of iron R = 0.1241 nm

atoms
atoms
19
= 1.2 x 10
2 = 12.1
2
nm
m2
Chapter 4 - 40

Planar Density of (111) Iron

Solution (cont): (111) plane

1 atom in plane/ unit surface cell

2a

atoms in plane

nit

atoms above plane

rep

ea

tu

atoms below plane

2D

area 2 ah 3 a 2 3
atoms
2D repeat unit

Planar Density =
area
2D repeat unit

1
16 3
3

atoms =
= 7.0
2
R

3
a
2

nm

4 3
R
3

16 3 2
R
3

0.70 x 1019

atoms
m2
Chapter 4 - 41

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 4 - 42

X-Rays to Determine Crystal Structure

Incoming X-rays diffract from crystal
d planes.

tg
u
o

ng
i
o

ys
a
-r

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

or

1
g

in
2
m
co s
i n r ay
X-

extra
distance
travelled
by wave 2

et
ec
t

reflections must
be in phase for
a detectable signal
Adapted from Fig. 4.29,
Callister & Rethwisch 9e.

spacing
between
planes

X-ray
intensity
(from
detector)

n
2 sin c

c
Chapter 4 - 43

X-Ray Diffraction Pattern

z

Intensity (relative)

c
a
x

c
b

y (110)

a
x

c
b

a
x

(211)

(200)

Diffraction angle 2

Diffraction pattern for polycrystalline -iron (BCC)

Adapted from Fig. 3.22, Callister 8e.

Chapter 4 - 44

Summary
Common metallic crystal structures are FCC, BCC, and
HCP. Coordination number and atomic packing factor
are the same for both FCC and HCP crystal 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).
Interatomic bonding in ceramics is ionic and/or covalent.
Ceramic crystal structures are based on:
-- maintaining charge neutrality
-- cation-anion radii ratios.
Some materials can have more than one crystal structure.
This is referred to as polymorphism (or allotropy).
X-ray diffraction is used for crystal structure and
interplanar spacing determinations.
Chapter 4 - 45