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
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. 4.2 (a),
Callister & Rethwisch 9e.
Chapter 4 - 5
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
VMSE Screenshot BCC Unit Cell

Chapter 4 - 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. 4.1(a), Callister & a
Rethwisch 9e.

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

Adapted from Fig. 3.1, Callister & Rethwisch 9e.

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

Chapter 4 - 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 9e. 4 3
unit cell 4 ( 2a/4 )
3 atom
APF =
3 volume
a
unit cell
Chapter 4 - 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

Chapter 4 - 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. 4.3(a),
Callister & Rethwisch 9e.

Coordination # = 12 6 atoms/unit cell

APF = 0.74 ex: Cd, Mg, Ti, Zn
c/a = 1.633
Chapter 4 - 12
VMSE Screenshot Stacking Sequence and Unit
Cell for HCP

Chapter 4 - 13
 Theoretical Density, r

Mass of Atoms in Unit Cell

Density = r =
Total Volume of Unit Cell

nA
r =
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

Chapter 4 - 14
 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. 4.1(a), Callister &
Rethwisch 9e.
atoms
g
unit cell 2 52.00 theoretical = 7.18 g/cm3
mol
r= actual = 7.19 g/cm3
a 3 6.022 x 1023
volume atoms
unit cell mol
Chapter 4 - 15
 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 - 16
 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 - 17
 Factors that Determine Crystal Structure
1. Relative sizes of ions Formation of stable structures:
--maximize the # of oppositely charged ion neighbors.
- - - - - -
+ + +
Adapted from Fig. 4.4,
Callister & Rethwisch 9e.
- - - - - -
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 Chapter 4 - 18
 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 Coord. ZnS
r anion Number (zinc blende)
Adapted from Fig. 4.7,
< 0.155 2 linear Callister & Rethwisch 9e.

0.155 - 0.225 3 triangular NaCl

(sodium
0.225 - 0.414 4 tetrahedral chloride)
Adapted from Fig. 4.5,
Callister & Rethwisch 9e.

0.414 - 0.732 6 octahedral CsCl

(cesium
chloride)
0.732 - 1.0 8 cubic Adapted from Fig. 4.6,
Adapted from Table 4.3, Callister & Rethwisch 9e.
Callister & Rethwisch 9e.
Chapter 4 - 19
 Computation of Minimum Cation-Anion
Radius Ratio
Determine minimum rcation/ranion for an octahedral site
(C.N. = 6)

a = 2ranion
2ranion + 2rcation = 2 2ranion

ranion + rcation = 2ranion rcation = ( 2 -1)ranion

rcation
= 2 - 1 = 0.414
ranion
Chapter 4 - 20
 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 - 21
 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 rcation 0.077
=
Fe 2+ 0.077 ranion 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 4.4,
F- 0.133 Callister & Rethwisch 9e.

Chapter 4 - 22
 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 - 23
 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 - 24
 AX Crystal Structures
AXType Crystal Structures include NaCl, CsCl, and zinc blende

Cesium Chloride structure:

Since 0.732 < 0.939 < 1.0,

cubic sites preferred

Fig. 4.6, Callister & Rethwisch 9e.

So each Cs+ has 8 neighbor Cl-

Chapter 4 - 25
 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 - 26
 ABX3 Crystal Structures
Perovskite structure

Ex: complex oxide

BaTiO3

Fig. 4.9, Callister &

Rethwisch 9e.

Chapter 4 - 27
VMSE Screenshot Zinc Blende Unit Cell

Chapter 4 - 28
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 - 29
 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
less dense packing 3
Diamond
Si nitride
Aluminum Glass -soda
often lighter elements Concrete
Silicon PTFE
Glass fibers
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, 9e.

Chapter 4 - 30
 Silicate Ceramics
Most common elements on earth are Si & O

Si4+

O2-

Figs. 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 - 31
 Silicates
Bonding of adjacent SiO44- accomplished by the
sharing of common corners, edges, or faces

Adapted from Fig.

4.13, Callister &
Rethwisch 9e.
Mg2SiO4 Ca2MgSi2O7

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

1. maintain charge neutrality, and
2. ionically bond SiO44- to one another
Chapter 4 - 32
 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
O2- impurity ions such as Na+, Ca2+,
Al3+, and B3+

Quartz is crystalline
Na +
SiO2:
Si 4+
O2-

(soda glass)
Adapted from Fig. 4.12,
Callister & Rethwisch 9e.

Chapter 4 - 33
 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 - 34
 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 - 35
 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
Fig. 4.17, Callister &
hard surface coatings Rethwisch 9e.
used for cutting tools,
medical devices, etc.

Chapter 4 - 36
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 - 37
 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 - 38
 Crystals as Building Blocks
Some engineering applications require single crystals:
-- diamond single -- turbine blades
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.
(Courtesy P.M. Anderson)

Chapter 4 - 39
 Polycrystals Anisotropic
Most engineering materials are polycrystals.

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. Isotropic

Each "grain" is a single crystal.
If grains are randomly oriented,
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 - 40
 Single vs Polycrystals
Single Crystals E (diagonal) = 273 GPa
Data from Table 3.3,
-Properties vary with Callister & Rethwisch 9e.
(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, 1989.)

of elasticity (E) in BCC iron:

E (edge) = 125 GPa
Polycrystals
-Properties may/may not 200 m Adapted from Fig.
6.19(b), Callister &
vary with direction. Rethwisch 9e.
[Fig. 6.19(b) is courtesy of
-If grains are randomly L.C. Smith and C. Brady, the
National Bureau of
oriented: isotropic. Standards, Washington, DC
(now the National Institute of
Standards and Technology,
(Epoly iron = 210 GPa) Gaithersburg, MD).]

-If grains are textured,

anisotropic.

Chapter 4 - 41
 Polymorphism
Two or more distinct crystal structures for the same
material (allotropy/polymorphism)
iron system
titanium
liquid
, -Ti
1538
BCC C
-Fe
carbon
diamond, graphite 1394
FCC C
-Fe
912C
BCC -Fe

Chapter 4 - 42
 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
Adapted from
Fig. 3.1(a),
length 2a
Callister &
Rethwisch 9e.

Chapter 4 - 43
 Planar Density of (100) Iron
Solution: At T < 912C iron has the BCC structure.
2D repeat unit

(100) 4 3
a= 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.] Radius of iron R = 0.1241 nm
atoms
2D repeat unit 1
1 atoms atoms
19
Planar Density = = 2 = 12.1 = 1.2 x 10
a2 4 3 nm 2 m2
area R
3
2D repeat unit
Chapter 4 - 44
 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

3
h= a
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
nm 2 m2
area 16 3 2
R
2D repeat unit 3
Chapter 4 - 45
VMSE Screenshot Atomic Packing
(111) Plane for BCC

Chapter 4 - 46
 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 - 47
 X-Rays to Determine Crystal Structure
Incoming X-rays diffract from crystal planes.

reflections must
be in phase for
a detectable signal
extra
distance
Adapted from Fig. 4.29,
travelled Callister & Rethwisch 9e.
by wave 2 spacing
d between
planes

Measurement of X-ray
n
critical angle, c, intensity d=
(from 2 sin c
allows computation of
detector)
planar spacing, d.

c
Chapter 4 - 48
 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. 3.22, Callister 8e.

Chapter 4 - 49
 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 - 50
 ANNOUNCEMENTS
Reading:

Core Problems:

Self-help Problems:

Chapter 4 - 51