SUMMARY: BONDING

Type Bond Energy Comments

Ionic Large! Nondirectional (ceramics)

Variable Directional
Covalent large-Diamond semiconductors, ceramics
small-Bismuth polymer chains)

Variable
Metallic large-Tungsten Nondirectional (metals)
small-Mercury
Directional
Secondary smallest inter-chain (polymer)
inter-molecular
 PROPERTIES FROM BONDING: TM
Bond length, r Melting Temperature, Tm
F
F Energy (r)
r

Bond energy, Eo ro
r
Energy (r)
smaller Tm
unstretched length
ro larger Tm
r
E o= Tm is larger if Eo is larger.
bond energy
 PROPERTIES FROM BONDING: E
Elastic modulus, Ecross
sectional
length, L o
area A o
Elastic modulus
undeformed F L
L =E
Ao Lo
deformed F

E ~ curvature at ro
Energy

unstretched length
ro E is larger if Eo is larger.
r
smaller Elastic Modulus

larger Elastic Modulus

 PROPERTIES FROM BONDING:
Coefficient of thermal expansion,
length, L o coeff. thermal expansion
unheated, T1
L L
=(T2-T 1)
heated, T2 Lo

~ symmetry at ro
Energy

ro
r is larger if Eo is smaller.
larger

smaller
 SUMMARY: PRIMARY BONDS
Ceramics Large bond energy
(Ionic & covalent bonding): large Tm
large E
small

Metals Variable bond energy

(Metallic bonding): moderate Tm
moderate E
moderate

Polymers Directional Properties

(Covalent & Secondary): Secondary bonding dominates
small T
small E
large
 CHAPTER 3: Structures of
Metals and Ceramics

ISSUES TO ADDRESS...
How do atoms assemble into solid structures?

How do the structures of ceramic

materials differ from those of metals?

How does the density of a material depend on

its structure?
When do material properties vary with the
sample (i.e., part) orientation?

1
 ENERGY AND PACKING
Non dense, random packing Energy

typical neighbor
bond length

typical neighbor r
bond energy

Dense, regular packing Energy

typical neighbor
bond length

typical neighbor r
bond energy

Dense, regular-packed structures tend to have

lower energy.
2
 METALLIC CRYSTALS
tend to be densely packed.
have several 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.

have the simplest crystal structures. 74

elements
have the simplest crystal structures BCC, FCC
and HCP
We will look at three such structures...
3
 The crystal lattice

A point lattice is made up of regular,

repeating points in space. An atom or
group of atoms are tied to each lattice
point
14 different point lattices, called Bravais lattices, make up the crystal system.
The lengths of the sides, a, b, and c, and the angles between them can vary for
a particular unit cell.
Three simple lattices that describe metals are Face Centered Cubic (FCC) Body
Centered Cubic (BCC) and Hexagonal Close Packed (HCP)
 SIMPLE CUBIC STRUCTURE (SC)
Rare due to poor packing (only Po has this structure)
Close-packed directions are cube edges.

Coordination # = 6
(# nearest neighbors)

Click on image to animate

(Courtesy P.M. Anderson)

4
 ATOMIC PACKING FACTOR
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. 3.19,
Callister 6e. 5
 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.

Coordination # = 12

Adapted from Fig. 3.1(a),

Click on image to animate Callister 6e.

(Courtesy P.M. Anderson)

6
 ATOMIC PACKING FACTOR: FCC
APF for a body-centered cubic structure = 0.74
Close-packed directions:
length = 4R
= 2a
Unit cell contains:
6 x 1/2 + 8 x 1/8
=4 atoms/unit cell
a
Adapted from
Fig. 3.1(a),
Callister 6e. atoms volume
4 3
unit cell 4 ( 2a/4)
3 atom
APF =
3 volume
a
unit cell
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.

Coordination # = 8

Adapted from Fig. 3.2,

Click on image to animate Callister 6e.

(Courtesy P.M. Anderson) 8

 ATOMIC PACKING FACTOR: BCC
APF for a body-centered cubic structure = 0.68
Close-packed directions:
length = 4R
= 3a
Unit cell contains:
1 + 8 x 1/8
=2 atoms/unit cell
R
Adapted from a
Fig. 3.2,
Callister 6e. atoms volume
4
unit cell 2 ( 3a/4)3
3 atom
APF =
volume
a3
unit cell
9
 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,
Callister 6e.

Coordination # = 12
APF = 0.74

10
 THEORETICAL DENSITY,
#atoms/unit cell Atomic weight (g/mol)

nA
Volume/unit cell Vc NA Avogadro's number
(cm3/unit cell) (6.023 x 1023 atoms/mol)

Example: Copper
Data from Table inside front cover of Callister (see next slide):
crystal structure = FCC: 4 atoms/unit cell
atomic weight = 63.55 g/mol (1 amu = 1 g/mol)
atomic radius R = 0.128 nm (1 nm = 10 -7 cm)
Vc = a3 ; For FCC, a = 4R/ 2 V; c = 4.75 x 10-23cm3
3
Result: theoreticalCu = 8.89 g/cm
Compare to actual:Cu = 8.94 g/cm3
11
Characteristics of Selected Elements at 20C
At. Weight Density Crystal Atomic radius
Element Symbol (amu) (g/cm3) Structure (nm)
Aluminum Al 26.98 2.71 FCC 0.143
Argon Ar 39.95 ------ ------ ------
Barium Ba 137.33 3.5 BCC 0.217
Beryllium Be 9.012 1.85 HCP 0.114
Boron B 10.81 2.34 Rhomb ------ Adapted from
Table, "Charac-
Bromine Br 79.90 ------ ------ ------ teristics of
Cadmium Cd 112.41 8.65 HCP 0.149 Selected
Calcium Ca 40.08 1.55 FCC 0.197 Elements",
inside front
Carbon C 12.011 2.25 Hex 0.071 cover,
Cesium Cs 132.91 1.87 BCC 0.265 Callister 6e.
Chlorine Cl 35.45 ------ ------ ------
Chromium Cr 52.00 7.19 BCC 0.125
Cobalt Co 58.93 8.9 HCP 0.125
Copper Cu 63.55 8.94 FCC 0.128
Flourine F 19.00 ------ ------ ------
Gallium Ga 69.72 5.90 Ortho. 0.122
Germanium Ge 72.59 5.32 Dia. cubic 0.122
Gold Au 196.97 19.32 FCC 0.144
Helium He 4.003 ------ ------ ------
Hydrogen H 1.008 ------ ------ ------ 12
 DENSITIES OF MATERIAL
CLASSES Graphite/
metalsceramicspolymers Metals/
Ceramics/ Polymers
Composites/
Alloys fibers
Semicond
Why? 30
Based on data in Table B1, Callister
Platinum
Metals have... 20 Gold, W
Tantalum
*GFRE, CFRE, & AFRE are Glass,
Carbon, & Aramid Fiber-Reinforced
close-packing Epoxy composites (values based on
60% volume fraction of aligned fibers
(metallic bonding) 10 Silver, Mo
Cu,Ni
in an epoxy matrix).

(g/cm3)
large atomic mass Steels
Tin, Zinc
Zirconia
Ceramics have... 5
Titanium
4 Al oxide
less dense packing Diamond
Si nitride
3
(covalent bonding) Aluminum Glass -soda
Concrete
Glass fibers
Silicon PTFE
often lighter elements 2 Magnesium Graphite
GFRE*
Carbon fibers
Silicone CFRE *
Polymers have... PVC
PET
Aramid fibers
AFRE *
poor packing 1 PC
HDPE, PS
PP, LDPE
(often amorphous)
lighter elements (C,H,O) 0.5 Wood
Composites have... 0.4
0.3
intermediate values Data from Table B1, Callister 6e.
13
 CERAMIC BONDING
Bonding:
--Mostly ionic, some covalent.
--% ionic character increases with difference in
electronegativity.
Large vs small ionic bond character:
H
2.1
CaF 2: large He
-
Li C F
1.0
Be
1.5 SiC: small 2.5 4.0
Ne
-
Na Mg Si Cl Ar
0.9 1.2 1.8 3.0 -
K Ca Ti Cr Fe Ni Zn As Br Kr
0.8 1.0 1.5 1.6 1.8 1.8 1.8 2.0 2.8 -
Rb Sr I Xe
0.8 1.0 2.5 -
Cs Ba At Rn
0.7 0.9 2.2 -
Fr Ra
0.7 0.9 Table of Electronegativities
Adapted from Fig. 2.7, Callister 6e. (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. 14
 IONIC BONDING & STRUCTURE
Charge Neutrality:
--Net charge in the F-
structure should CaF 2: Ca 2+ +
cation anions
be zero.
F-

--General form: A mXp

m, p determined by charge neutrality

Stable structures:
--maximize the # of nearest oppositely charged neighbors.
- - - - - -
+ + +
Adapted from Fig.
12.1, Callister 6e.
- - - - - -
unstable stable stable 15
 COORDINATION # AND IONIC

RADII
Coordination # increases with
rcation
ranion
Issue: How many anions can you
arrange around a cation?

rcation ZnS
Coord #
ranion (zincblende)
Adapted from Fig. 12.4,
< .155 2 Callister 6e.

.155-.225 3 NaCl
(sodium
.225-.414 4 chloride)
Adapted from Fig. 12.2,
Callister 6e.
.414-.732 6
CsCl
(cesium
.732-1.0 8 chloride)
Adapted from Fig. 12.3,
Adapted from Table Callister 6e.
12.2, Callister 6e.
16
 EX: PREDICTING 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
Anion
--structure = NaCl
O2- 0.140
Cl - 0.181
F-
Data from Table 12.3,
0.133 Callister 6e.
17
 AmXp STRUCTURES
rcation 0.100
Consider CaF2 : r 0.8
anion 0.133
Based on this ratio, coord # = 8 and structure = CsCl.
Result: CsCl structure w/only half the cation sites
occupied.
Only half the cation sites
are occupied since
#Ca2+ ions = 1/2 # F-
ions.

Adapted from Fig. 12.5,

Callister 6e.

18
 DEMO: HEATING AND
COOLING OF AN IRON WIRE
The same atoms can
Demonstrates "polymorphism" have more than one
crystal structure.
Temperature, C
Liquid
1536
BCC Stable
1391
longer
heat up
FCC Stable
shorter!
914 longer!
BCC Stable
cool down
Tc 768 magnet falls off
shorter
19
 FCC STACKING SEQUENCE
ABCABC... Stacking Sequence
2D Projection
A
B B
C
A
A sites B B B
C C
B sites B B
C sites

A
FCC Unit Cell B
C

20
 STRUCTURE OF COMPOUNDS: NaCl
Compounds: Often have similar close-packed structures.
Structure of NaCl Close-packed directions
--along cube edges.

Click on image to animate Click on image to animate

(Courtesy P.M. Anderson) (Courtesy P.M. Anderson)

21
Diamond, BeO and GaAs are examples of FCC structures with two atoms per lattice
point
 CRYSTALS AS BUILDING BLOCKS
Some engineering applications require single crystals:
--diamond single --turbine blades
crystals for abrasives Fig. 8.30(c), Callister 6e.
(Fig. 8.30(c) courtesy
(Courtesy Martin of Pratt and Whitney).
Deakins,
GE Superabrasives,
Worthington, OH. Used
with permission.)

Crystal properties reveal features

of atomic structure.
--Ex: Certain crystal planes in quartz
fracture more easily than others.

(Courtesy P.M. Anderson)

22
 POLYCRYSTALS
Most engineering materials are polycrystals.

Adapted from Fig. K,

color inset pages of
Callister 6e.
(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 crystals are randomly oriented,
overall component properties are not directional.
Crystal sizes typ. range from 1 nm to 2 cm
(i.e., from a few to millions of atomic layers).
23
 SINGLE VS POLYCRYSTALS
Single Crystals
-Properties vary with
direction: anisotropic.
-Example: the modulus
of elasticity (E) in BCC iron:
E (edge) = 125 GPa
Polycrystals
-Properties may/may not
vary with direction.
-If grains are randomly
oriented: isotropic.
(Epoly iron = 210 GPa)
-If grains are textured,
anisotropic.
E (diagonal) = 273 GPa
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.)
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].)
24
 MATERIALS AND PACKING
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
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.

26
 GLASS STRUCTURE
Basic Unit: Glass is amorphous
4- Amorphous structure
Si04 tetrahedron occurs by adding impurities
Si 4+ (Na+,Mg2+,Ca2+, Al3+)
O2- Impurities:
interfere with formation of
crystalline structure.
Quartz is crystalline Na+
SiO2: Si 4+
O2-

(soda glass)
Adapted from Fig.
12.11, Callister, 6e.

28
 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 geometry (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.

27