Chapter 3

Structures of Metals and Ceramics

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 Crystal Structures

FCC BCC HCP

(Face-Centered Cubic) (Body-Centered Cubic) (Hexagonal Close-Packed)

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 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 # :
Nearest-neighbor or touching atoms
FCC: 12

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FCC (Face-Centered Cubic)

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BODY CENTERED CUBIC STRUCTURE
(BCC)

Unit cell Reduced-sphere unit cell

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BCC (Body-Centered Cubic)

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BCC (Body-Centered Cubic)

Unit cell for BCC

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 HCP (Hexagonal Close-Packed) Structure

Reduced-sphere unit cell

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 Stacking sequence

A A A A A A
B B B B
C
A A A A A A
A A A
B B B B B B
C C
A A A A AA A
B B B B
A A A A A A A A

ABCABC….: FCC ABAB…..: HCP (see next slide)

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 A
B B
C
A
A sites B B B
C C
B sites B B
C sites

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 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

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HCP

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FCC

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 ATOMIC PACKING FACTOR

Volume of atoms in unit cell*

APF =
Volume of unit cell
*assume hard spheres
Unit Cell
Unit cellcontains
contains:
Close-packed directions:
6 x 1/2 + 8 x 1/8
length = 4R
= 4 atoms/unit cell
= 2a
atoms volume
4
unit cell 4 π ( 2a/4)3
3 atom
APF =
volume
a a3
unit cell
• APF for a face-centered cubic structure = 0.74, which is the maximum
packing possible for spheres all having the same diameter.
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 THEORETICAL DENSITY, ρ
# atoms/unit cell Atomic weight (g/mol)

ρ= nA
Volume/unit cell VcNA Avogadro's number
(cm3/unit cell) (6.023 x 10 23 atoms/mol)

Example: Copper
Data from Table inside front cover of the textbook:
• 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 = 10-7cm)
Vc = a3 ; For FCC, a = 4R/ 2 ; Vc = 4.75 x 10-23cm3
Result: theoretical ρCu = 8.89 g/cm3
Compare to actual: ρCu = 8.94 g/cm3
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 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
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 DENSITIES OF MATERIAL CLASSES
Graphite/
ρmetals ρceramics ρpolymers Metals/
Alloys
Ceramics/ Polymers
Composites/
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).

• large atomic mass Steels

ρ (g/cm3)
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
PTFE
• often lighter elements 2 Magnesium
Silicon
Graphite
GFRE*
Carbon fibers
CFRE*
Polymers have... Silicone
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
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 CERAMIC BONDING
• Bonding:
--Mostly ionic, some covalent.
--% ionic character increases with difference in
electronegativity.
• Large vs small ionic bond character:
H
2.1
CaF2: 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.

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 IONIC BONDING & STRUCTURE
• Charge Neutrality:
--Net charge in the F-
structure should CaF2: Ca2+ +
cation anions
be zero.
F-

--General form: AmXp

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
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 COORDINATION # AND IONIC RADII
rcation
• Coordination # increases with r
Issue: How many anions can you anion
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.
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 Rock Salt (NaCl) Structure

FCC

NaCl

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Cesium Chloride (CsCl) Structure

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Zinc Blende (ZnS) Structure

Diamond

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 AmXp STRUCTURES
r cation 0.100
• Consider CaF2 : = ≈ 0.8
r 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.

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Fluorite (CaF2) Structure

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Silicon-oxygen tetrahedron

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 Polymorphism and Allotropy
Polymorphism: having more than one crystal structure
Allotropy: polymorphism for elemental solids

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A Unit Cell

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Point Coordinates

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Point Coordinates

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Point Coordinates

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Crystallographic Directions

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Crystallographic Planes and Miller Indices

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Crystallographic Planes and Miller Indices

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Crystallographic Planes and Miller Indices

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Atomic Arrangements

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Atomic Arrangements

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• Single Crystals

• Polycrystals

• Noncrystalline materials (Amorphous materials)

• Grain and Grain Boundary (Fig. 3.35)

Si Oxygen

noncrystalline SiO2

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Grain and Grain Boundary

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 Classification of Solid Materials

Single crystals

Crystalline

polycrystalline

Solid materials

Noncrystalline

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X-Ray Diffraction and Bragg’s Law

Eq. 3.15 and Eq. 3.16

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X-Ray Diffractometer

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Family of Lattice Planes

d hkl = a
h 2 + k 2 +l 2
a : lattice parameter
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X-Ray Diffraction and Bragg’s Law

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