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ISSUES TO ADDRESS...
How do atoms assemble into solid structures
in metallic, ceramic and polymeric materials?
How do the structures of ceramic materials
differ from those of metals?
vs.
Chapter 4 -
Chapter 4 -
a
R=0.5a
close-packed directions
contains 8 x 1/8 =
1 atom/unit cell
APF =
volume
atom
4
(0.5a) 3
1
3
a3
volume
unit cell
Chapter 4 -
Coordination # = 8
a
2a
From
Fig. 4.2(a)
Callisters Materials
Science and
Engineering,
Adapted Version.
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 -
Coordination # = 12
Chapter 4 -
2a
a
From
Fig. 4.1(a),
Callisters Materials Science
and Engineering,
Adapted Version.
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
A
B
C
Chapter 4 -
10
2D Projection
A sites
Top layer
B sites
Middle layer
A sites
Bottom layer
Coordination # = 12
APF = 0.74
c/a = 1.633
6 atoms/unit cell
ex: Cd, Mg, Ti, Zn
Chapter 4 -
11
Theoretical Density,
Density = =
=
where
nA
VC NA
12
Theoretical Density,
Ex: Cr (BCC)
A = 52.00 g/mol
R = 0.125 nm
n=2
R
atoms
unit cell
=
volume
unit cell
a
2 52.00
a3 6.023 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
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
Composites have...
intermediate values
Metals/
Alloys
20
Platinum
Gold, W
Tantalum
10
Silver, Mo
Cu,Ni
Steels
Tin, Zinc
5
4
3
2
1
Titanium
Aluminum
Magnesium
Graphite/
Ceramics/
Semicond
Composites/
fibers
Polymers
PTFE
Silicone
PVC
PET
PC
HDPE, PS
PP, LDPE
0.5
0.4
0.3
Data from Table B1
Callisters Materials Science and Engineering,
Adapted Version.
Glass fibers
GFRE*
Carbon fibers
CFRE*
Aramid fibers
AFRE*
Wood
Chapter 4 -
14
Linear Density
Linear Density of Atoms LD =
[110]
Number of atoms
Unit length of direction vector
# atoms
LD
length
2
2a
3.5 nm 1
Chapter 4 -
15
Chapter 4 -
16
(100)
atoms
2D repeat unit
Planar Density =
area
2D repeat unit
1
a2
4 3
R
3
1
4 3
R
3
atoms
atoms
19
= 1.2 x 10
2 = 12.1
2
nm
m2
Chapter 4 -
17
2a
atoms in plane
nit
r ep
ea
tu
2D
4 3
area 2 ah 3 a 3
R
3
atoms
2D repeat unit
Planar Density =
area
2D repeat unit
1
16 3
3
atoms =
= 7.0
2
R
3
a
2
nm
16 3 2
R
3
0.70 x 1019
atoms
m2
Chapter 4 -
18
-Fe
Chapter 4 -
19
Chapter 4 -
20
Site Selection
Which sites will cations occupy?
1. Size of sites
does the cation fit in the site
2. Stoichiometry
if all of one type of site is full the
remainder have to go into other types of
sites.
3. Bond Hybridization
Chapter 4 -
21
unstable
Charge Neutrality:
stable
CaF 2 :
stable
Ca 2+ +
cation
Fanions
F-
A m Xp
m, p determined by charge neutrality
Chapter 4 -
22
r cation
Coordination # increases with r
anion
Coord
#
2
linear
0.155 - 0.225
triangular
0.225 - 0.414
TD
ZnS
(zincblende)
From Fig. 4.13
NaCl
(sodium
chloride)
From Fig. 4.11
0.414 - 0.732
OH
0.732 - 1.0
cubic
CsCl
(cesium
chloride)
From Fig. 4.12
Chapter 4 -
23
2ranion 2rcation 2a
a 2ranion
rcation ( 2 1)ranion
rcation
0.414
ranion
Chapter 4 -
24
Site Selection II
2. Stoichiometry
If all of one type of site is full the remainder have to go
into other types of sites.
25
26
0.140
0.181
0.133
Answer:
rcation 0.077
ranion 0.140
0.550
based on this ratio,
--coord # = 6
--structure = NaCl
Chapter 4 -
27
rNa = 0.102 nm
rCl = 0.181 nm
rNa/rCl = 0.564
cations prefer OH sites
Chapter 4 -
28
rO = 0.140 nm
Mg2+
rMg = 0.072 nm
rMg/rO = 0.514
cations prefer OH sites
29
AX Crystal Structures
AXType Crystal Structures include NaCl, CsCl, and zinc blende
rCs
rCl
0.170
0.939
0.181
Chapter 4 -
30
AX Crystal Structures
Zinc Blende structure
rZn2
rO 2
0.074
0.529 OH ??
0.140
31
32
33
Mechanical Properties
We know that ceramics are more brittle
than metals. Why?
Consider method of deformation (will
learn later in chapters on mechanical
properties Chapter 9 and 10)
slippage along slip planes
in ionic solids this slippage is very difficult
too much energy needed to move one anion
past another anion
Chapter 4 -
34
n( AC AA )
VC N A
Volume of unit cell
Chapter 4 -
35
Silicate Ceramics
Most common elements on earth are Si & O
Si4+
O2From Figs. 4.18 and 4.19
Callisters Materials Science
and Engineering
Adapted Version.
crystobalite
36
Amorphous Silica
Silica gels - amorphous SiO2
Si4+ and O2- not in well-ordered
lattice
Charge balanced by H+ (to form
OH-) at dangling bonds
very high surface area > 200
m2/g
Chapter 4 -
37
Silica Glass
Dense form of amorphous silica
Charge imbalance corrected with
counter cations such as Na+
Borosilicate glass is the pyrex glass
used in labs
better temperature stability & less brittle than
sodium glass
Chapter 4 -
38
Silicates
Combine SiO44- tetrahedra by having them
share corners, edges, or faces
Mg2SiO4
Ca2MgSi2O7
39
Layered Silicates
Layered silicates (clay
silicates)
SiO4 tetrahedra connected
together to form 2-D plane
40
Layered Silicates
Kaolinite clay alternates (Si2O5)2- layer with
Al2(OH)42+ layer
Chapter 4 -
41
Layered Silicates
Can change the counterions
this changes layer spacing
the layers also allow absorption of water
Micas KAl3Si3O10(OH)2
Bentonite
Chapter 4 -
42
Carbon Forms
Carbon black amorphous
surface area ca. 1000 m2/g
Diamond
tetrahedral carbon
hard no good slip planes
brittle can cut it
diamond films
hard surface coat tools,
medical devices, etc.
Chapter 4 -
43
Chapter 4 -
44
Carbon Forms
Fullerenes and Nanotubes
Fullerenes or carbon nanotubes
wrap the graphite sheet by curving into ball or tube
Buckminister fullerenes
Like a soccer ball C60 - also C70 + others
Chapter 4 -
45
Polymer Crystallinity
Ex: polyethylene unit cell
Crystals must contain
the polymer chains in
some way
Chain folded structure
10 nm
46
Polymer Crystallinity
Polymers rarely 100% crystalline
% Crystallinity: % of material
that is crystalline.
-- TS and E often increase
with % crystallinity.
-- Annealing causes
crystalline regions
to grow. % crystallinity
increases.
amorphous
region
From Fig. 14.11, Callister 6e.
(Fig. 14.11 is from H.W. Hayden, W.G. Moffatt,
and J. Wulff, The Structure and Properties of
Materials, Vol. III, Mechanical Behavior, John Wiley
and Sons, Inc., 1965.)
Chapter 4 -
47
48
Spherulite
surface
From Fig. 4.32
Callisters Materials Science and Engineering
Adapted Version.
Chapter 4 -
49
Chapter 4 -
50
g
ut
ng
i
o
g
in
m
co s
in ray
Xextra
distance
travelled
by wave 2
ys
a
r
X-
et
ec
to
r
Measurement of
critical angle, c,
allows computation of
planar spacing, d.
reflections must
be in phase for
a detectable signal
spacing
between
planes
X-ray
intensity
(from
detector)
n
2 sin c
Chapter 4 -
52
Intensity (relative)
c
a
x
y (110)
a
x
c
b
a
x
(211)
(200)
Diffraction angle 2
53
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).
Crystallographic directions and planes are related
to atomic linear densities and planar densities.
Some materials can have more than one crystal
structure. This is referred to as polymorphism (or
allotropy).
Chapter 4 -
54
SUMMARY
Ceramic materials have covalent & ionic bonding.
Ceramic structures are based on charge neutrality
Chapter 4 -
55
ANNOUNCEMENTS
Reading:
Core Problems:
Self-help Problems:
Chapter 4 -
56