Chapter 3-

ISSUES TO ADDRESS...
How do atoms assembIe into soIid structures?
(for now, focus on metaIs)
How does the density of a materiaI depend on
its structure?
When do materiaI properties vary with the
sampIe (i.e., part) orientation?
1
CHAPTER 3: CRYSTAL
STRUCTURES & PROPERTIES
Chapter 3- 2
Non dense, random packing
Dense, reguIar packing
Dense, reguIar-packed structures tend to have
Iower energy.
Energy
r
typicaI neighbor
bond Iength
typicaI neighbor
bond energy
Energy
r
typicaI neighbor
bond Iength
typicaI neighbor
bond energy
ENERGY AND PACKING
Chapter 3-
atoms pack in periodic, 3D arrays
typicaI of:
3
CrystaIIine materiaIs...
-metaIs
-many ceramics
-some poIymers
atoms have no periodic packing
occurs for:
NoncrystaIIine materiaIs...
-compIex structures
-rapid cooIing
Si Oxygen
crystaIIine SiO2
noncrystaIIine SiO2
"Amorphous" = NoncrystaIIine
Adapted from Fig. 3.18(b),
CaIIister 6e.
Adapted from Fig. 3.18(a),
CaIIister 6e.
MATERIALS AND PACKING
Chapter 3- 4
tend to be denseIy packed.
have severaI reasons for dense packing:
-TypicaIIy, onIy one eIement is present, so aII atomic
radii are the same.
-MetaIIic bonding is not directionaI.
-Nearest neighbor distances tend to be smaII in
order to Iower bond energy.
have the simpIest crystaI structures.
We wiII Iook at three such structures...
METALLIC CRYSTALS
Chapter 3- 5
Rare due to poor packing (onIy Po has this structure)
CIose-packed directions are cube edges.
Coordination # = 6
(# nearest neighbors)
(Courtesy P.M. Anderson)
SIMPLE CUBIC STRUCTURE (SC)
Chapter 3- 6
APF =
VoIume of atoms in unit ceII*
VoIume of unit ceII
*assume hard spheres
APF for a simpIe cubic structure = 0.52
APF =
a
3
4
3
6(0.5a)
3
1
atoms
unit ceII
atom
voIume
unit ceII
voIume
cIose-packed directions
a
R=0.5a
contains 8 x 1/8 =
1 atom/unit ceII
Adapted from Fig. 3.19,
CaIIister 6e.
ATOMIC PACKING FACTOR
Chapter 3-
Coordination # = 8
7
Adapted from Fig. 3.2,
CaIIister 6e.
(Courtesy P.M. Anderson)
CIose packed directions are cube diagonaIs.
--Note: AII atoms are identicaI; the center atom is shaded
differentIy onIy for ease of viewing.
BODY CENTERED CUBIC
STRUCTURE (BCC)
Chapter 3-
a
R
8
APF for a body-centered cubic structure = 0.68
CIose-packed directions:
Iength = 4R
= 3 a
Unit ceII contains:
1 + 8 x 1/8
= 2 atoms/unit ceII
Adapted from
Fig. 3.2,
CaIIister 6e.
ATOMIC PACKING FACTOR: BCC
APF =
a
3
4
3
6( 3a/4)
3
2
atoms
unit ceII
atom
voIume
unit ceII
voIume
Chapter 3- 9
Coordination # = 12
Adapted from Fig. 3.1(a),
CaIIister 6e.
(Courtesy P.M. Anderson)
CIose packed directions are face diagonaIs.
--Note: AII atoms are identicaI; the face-centered atoms are shaded
differentIy onIy for ease of viewing.
FACE CENTERED CUBIC
STRUCTURE (FCC)
Chapter 3-
APF =
a
3
4
3
6( 2a/4)
3
4
atoms
unit ceII
atom
voIume
unit ceII
voIume
Unit ceII contains:
6 x 1/2 + 8 x 1/8
= 4 atoms/unit ceII
a
10
APF for a body-centered cubic structure = 0.74
CIose-packed directions:
Iength = 4R
= 2 a
Adapted from
Fig. 3.1(a),
CaIIister 6e.
ATOMIC PACKING FACTOR: FCC
Chapter 3- 11
ABCABC... Stacking Sequence
2D Projection
A sites
B sites
C sites
B
B
B
B
B
B B
C
C
C
A
A
FCC Unit CeII
A
B
C
FCC STACKING SEQUENCE
Chapter 3- 12
Coordination # = 12
ABAB... Stacking Sequence
APF = 0.74
3D Projection 2D Projection
A sites
B sites
A sites
Bottom Iayer
MiddIe Iayer
Top Iayer
Adapted from Fig. 3.3,
CaIIister 6e.
HEXAGONAL CLOSE-PACKED
STRUCTURE (HCP)
Chapter 3- 13
Compounds: Often have simiIar cIose-packed structures.
CIose-packed directions
--aIong cube edges.
Structure of NaCI
(Courtesy P.M. Anderson) (Courtesy P.M. Anderson)
STRUCTURE OF COMPOUNDS: NaCI
Chapter 3- 14
ExampIe: Copper
8
n A
V
c
N
A
# atoms/unit ceII Atomic weight (g/moI)
VoIume/unit ceII
(cm
3
/unit ceII)
Avogadro's number
(6.023 x 10
23
atoms/moI)
Data from TabIe inside front cover of CaIIister (see next sIide):
crystaI structure = FCC: 4 atoms/unit ceII
atomic weight = 63.55 g/moI (1 amu = 1 g/moI)
atomic radius R = 0.128 nm (1 nm = 10 cm)
-7
V
c
= a
3
; For FCC, a = 4R/ 2 ; V
c
= 4.75 x 10
-23
cm
3
Compare to actuaI: 8
Cu
= 8.94 g/cm
3
ResuIt: theoreticaI 8
Cu
= 8.89 g/cm
3
THEORETICAL DENSITY, 8
Chapter 3- 15
EIement
AIuminum
Argon
Barium
BeryIIium
Boron
Bromine
Cadmium
CaIcium
Carbon
Cesium
ChIorine
Chromium
CobaIt
Copper
FIourine
GaIIium
Germanium
GoId
HeIium
Hydrogen
SymboI
AI
Ar
Ba
Be
B
Br
Cd
Ca
C
Cs
CI
Cr
Co
Cu
F
Ga
Ge
Au
He
H
At. Weight
(amu)
26.98
39.95
137.33
9.012
10.81
79.90
112.41
40.08
12.011
132.91
35.45
52.00
58.93
63.55
19.00
69.72
72.59
196.97
4.003
1.008
Atomic radius
(nm)
0.143
------
0.217
0.114
------
------
0.149
0.197
0.071
0.265
------
0.125
0.125
0.128
------
0.122
0.122
0.144
------
------
Density
(g/cm
3
)
2.71
------
3.5
1.85
2.34
------
8.65
1.55
2.25
1.87
------
7.19
8.9
8.94
------
5.90
5.32
19.32
------
------
CrystaI
Structure
FCC
------
BCC
HCP
Rhomb
------
HCP
FCC
Hex
BCC
------
BCC
HCP
FCC
------
Ortho.
Dia. cubic
FCC
------
------
Adapted from
TabIe, "Charac-
teristics of
SeIected
EIements",
inside front
cover,
CaIIister 6e.
Characteristics of SeIected EIements at 20C
Chapter 3-
8
metaIs
8
ceramics
8
poIymers

16
8

(
g
/
c
m
3
)
Graphite/
Ceramics/
Semicond
MetaIs/
AIIoys
Composites/
fibers
PoIymers
1
2
20
30
Based on data in TabIe B1, CaIIister
*GFRE, CFRE, & AFRE are GIass,
Carbon, & Aramid Fiber-Reinforced
Epoxy composites (vaIues based on
60% voIume fraction of aIigned fibers
in an epoxy matrix). 10
3
4
5
0.3
0.4
0.5
Magnesium
AIuminum
SteeIs
Titanium
Cu,Ni
Tin, Zinc
SiIver, Mo
TantaIum
GoId, W
PIatinum
Graphite
SiIicon
GIass-soda
Concrete
Si nitride
Diamond
AI oxide
Zirconia
HDPE, PS
PP, LDPE
PC
PTFE
PET
PVC
SiIicone
Wood
AFRE*
CFRE*
GFRE*
GIass fibers
Carbon fibers
Aramid fibers
Why?
MetaIs have...
cIose-packing
(metaIIic bonding)
Iarge atomic mass
Ceramics have...
Iess dense packing
(covaIent bonding)
often Iighter eIements
PoIymers have...
poor packing
(often amorphous)
Iighter eIements (C,H,O)
Composites have...
intermediate vaIues
Data from TabIe B1, CaIIister 6e.
DENSITIES OF MATERIAL CLASSES
Chapter 3- 17
Some engineering appIications require singIe crystaIs:
CrystaI properties reveaI features
of atomic structure.
(Courtesy P.M. Anderson)
--Ex: Certain crystaI pIanes in quartz
fracture more easiIy than others.
--diamond singIe
crystaIs for abrasives
--turbine bIades
Fig. 8.30(c), CaIIister 6e.
(Fig. 8.30(c) courtesy
of Pratt and Whitney).
(Courtesy Martin Deakins,
GE Superabrasives,
Worthington, OH. Used
with permission.)
CRYSTALS AS BUILDING BLOCKS
Chapter 3- 18
Most engineering materiaIs are poIycrystaIs.
Nb-Hf-W pIate with an eIectron beam weId.
Each "grain" is a singIe crystaI.
If crystaIs are randomIy oriented,
overaII component properties are not directionaI.
CrystaI sizes typ. range from 1 nm to 2 cm
(i.e., from a few to miIIions of atomic Iayers).
Adapted from Fig. K,
coIor inset pages of
CaIIister 6e.
(Fig. K is courtesy of
PauI E. DanieIson,
TeIedyne Wah Chang
AIbany)
1 mm
POLYCRYSTALS
Chapter 3- 19
SingIe CrystaIs
-Properties vary with
direction: anisotropic.
-ExampIe: the moduIus
of eIasticity (E) in BCC iron:
PoIycrystaIs
-Properties may/may not
vary with direction.
-If grains are randomIy
oriented: isotropic.
(E
poIy iron
= 210 GPa)
-If grains are textured,
anisotropic.
E (diagonaI) = 273 GPa
E (edge) = 125 GPa
200 3m
Data from TabIe 3.3,
CaIIister 6e.
(Source of data is
R.W. Hertzberg,
Deformation and
Fracture Mechanics of
Engineering MateriaIs,
3rd ed., John WiIey
and Sons, 1989.)
Adapted from Fig.
4.12(b), CaIIister 6e.
(Fig. 4.12(b) is
courtesy of L.C. Smith
and C. Brady, the
NationaI Bureau of
Standards,
Washington, DC [now
the NationaI Institute
of Standards and
TechnoIogy,
Gaithersburg, MD].)
SINGLE VS POLYCRYSTALS
Chapter 3-
d=n2/2sin7
c
x-ray
intensity
(from
detector)
7
7
c
20
Incoming X-rays diffract from crystaI pIanes.
Measurement of:
CriticaI angIes, 7
c
,
for X-rays provide
atomic spacing, d.
Adapted from Fig.
3.2W, CaIIister 6e.
X-RAYS TO CONFIRM CRYSTAL STRUCTURE
refIections must
be in phase to
detect signaI
spacing
between
pIanes
d
i
n
c
o
m
i
n
g

X
-
r
a
y
s
o
u
t
g
o
i
n
g

X
-
r
a
y
s
d
e
t
e
c
t
o
r
7
2
7
extra
distance
traveIIed
by wave "2"
"
1
"
"
2
"
"
1
"
"
2
"
Chapter 3- 21
Atoms can be arranged and imaged!
Carbon monoxide
moIecuIes arranged
on a pIatinum (111)
surface.
Photos produced from
the work of C.P. Lutz,
ZeppenfeId, and D.M.
EigIer. Reprinted with
permission from
InternationaI Business
Machines Corporation,
copyright 1995.
Iron atoms
arranged on a
copper (111)
surface. These
Kanji characters
represent the word
"atom".
SCANNING TUNNELING
MICROSCOPY
Chapter 3- 22
Demonstrates "poIymorphism"
The same atoms can
have more than one
crystaI structure.
DEMO: HEATING AND
COOLING OF AN IRON WIRE
Temperature, C
BCC StabIe
FCC StabIe
914
1391
1536
shorter
Ionger!
shorter!
Ionger
T
c
768
magnet faIIs off
BCC StabIe
Liquid
heat up
cooI down
Chapter 3-
Atoms may assembIe into crystaIIine or
amorphous structures.
We can predict the density of a materiaI,
provided we know the atomic weight, atomic
radius, and crystaI geometry (e.g., FCC,
BCC, HCP).
MateriaI properties generaIIy vary with singIe
crystaI orientation (i.e., they are anisotropic),
but properties are generaIIy non-directionaI
(i.e., they are isotropic) in poIycrystaIs with
randomIy oriented grains.
23
SUMMARY
Chapter 3-
Reading:
Core ProbIems:
SeIf-heIp ProbIems:
0
ANNOUNCEMENTS