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ISSUES TO ADDRESS...
Chapter 3 - 1
Energy and Packing
• Non dense, random packing Energy
typical neighbor
bond length
typical neighbor r
bond energy
typical neighbor
bond length
typical neighbor r
bond energy
Si Oxygen
Noncrystalline materials...
• atoms have no periodic packing
• occurs for: -complex structures
-rapid cooling
"Amorphous" = Noncrystalline noncrystalline SiO2
Adapted from Fig. 3.40(b),
Callister & Rethwisch 3e.
Chapter 3 - 3
Metallic Crystal Structures
• How can we stack metal atoms to minimize
empty space?
2-dimensions
vs.
Chapter 3 - 5
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)
QuickTime™ and a
Cinepak decompressor
are needed to see this picture.
2a
Close-packed directions:
Adapted from R length = 4R = 3 a
Fig. 3.2(a), Callister &
Rethwisch 3e.
a
atoms volume
4
unit cell 2 ( 3a/4) 3
3 atom
APF =
volume
a3
unit cell Chapter 3 - 9
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.
QuickTime™ and a
Cinepak decompressor
are needed to see this picture.
A
• FCC Unit Cell B
C
Chapter 3 - 12
Hexagonal Close-Packed Structure
(HCP)
• ABAB... Stacking Sequence
• 3D Projection • 2D Projection
nA
=
VC NA
Chapter 3 - 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. 3.2(a), Callister &
Rethwisch 3e.
atoms
g
unit cell 2 52.00 theoretical = 7.18 g/cm3
mol
= actual = 7.19 g/cm3
a3 6.022 x 1023
volume atoms
unit cell mol Chapter 3 - 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
Adapted from Fig. 2.7, Callister & Rethwisch 3e. (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. Chapter 3 - 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 3 - 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. 3.4,
Callister & Rethwisch 3e.
- - - - - -
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 3 - 18
Coordination # and Ionic Radii
r cation
• Coordination # increases with r
anion
To form a stable structure, how many anions can
surround around a cation?
r cation Coord ZnS
r anion # (zinc blende)
Adapted from Fig. 3.7,
< 0.155 2 linear Callister & Rethwisch 3e.
2ranion 2rcation 2a
a 2ranion
cation
2 1 0.414
anion
Chapter 3 - 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
Chapter 3 - 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
F-
Data from Table 3.4,
0.133 Callister & Rethwisch 3e.
Chapter 3 - 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
Chapter 3 - 23
MgO and FeO
MgO and FeO also have the NaCl structure
O2- rO = 0.140 nm
rMg/rO = 0.514
Chapter 3 - 24
AX Crystal Structures
AX–Type Crystal Structures include NaCl, CsCl, and zinc blende
Cs 0.170
0.939
Cl 0.181
Chapter 3 - 25
AX2 Crystal Structures
Fluorite structure
• Antifluorite structure –
positions of cations and
anions reversed
Adapted from Fig. 3.8,
Callister & Rethwisch 3e.
Chapter 3 - 26
ABX3 Crystal Structures
• Perovskite structure
Chapter 3 - 27
Density Computations for Ceramics
n(AC AA )
VC N A
Avogadro’s number
Volume of unit cell
Chapter 3 - 28
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
Diamond
• less dense packing 3 Si nitride
Aluminum Glass -soda Glass fibers
• often lighter elements Concrete
Silicon PTFE GFRE*
2
Polymers have... Magnesium Graphite
Silicone
Carbon fibers
CFRE*
Aramid fibers
PVC
• low packing density PET
PC
AFRE*
1
(often amorphous) HDPE, PS
PP, LDPE
• lighter elements (C,H,O)
0.5
Composites have... 0.4
Wood
Si4+
O2-
• Quartz is crystalline
Na +
SiO2: Si 4+
O2-
(soda glass)
Adapted from Fig. 3.41,
Callister & Rethwisch 3e.
Chapter 3 - 32
Layered Silicates
• Layered silicates (e.g., clays, mica,
talc)
– SiO4 tetrahedra connected
together to form 2-D plane
Chapter 3 - 33
Layered Silicates (cont)
• Kaolinite clay alternates (Si2O5)2- layer with Al2(OH)42+
layer
Chapter 3 - 35
Polymorphic Forms of Carbon (cont)
Graphite
– layered structure – parallel hexagonal arrays of
carbon atoms
Chapter 3 - 37
Crystals as Building Blocks
• Some engineering applications require single crystals:
-- diamond single -- turbine blades
crystals for abrasives Fig. 9.40(c), Callister &
Rethwisch 3e. (Fig. 9.40(c)
(Courtesy Martin Deakins,
courtesy of Pratt and
GE Superabrasives,
Whitney).
Worthington, OH. Used with
permission.)
Chapter 3 - 38
Polycrystals Anisotropic
• Most engineering materials are polycrystals.
Chapter 3 - 40
Polymorphism
• Two or more distinct crystal structures for the same
material (allotropy/polymorphism)
iron system
titanium
liquid
, -Ti
1538ºC
BCC -Fe
carbon
1394ºC
diamond, graphite
FCC -Fe
912ºC
BCC -Fe
Chapter 3 - 41
Crystal Systems
Unit cell: smallest repetitive volume which
contains the complete lattice pattern of a crystal.
7 crystal systems
14 crystal lattices
000
y
a b
x Point coordinates for unit cell
corner are 111
z 2c
x [uvw]
[110]
ex: linear density of Al in [110]
direction
a = 0.405 nm
# atoms
a 2
LD 3.5 nm 1
length 2a
Chapter 3 - 45
HCP Crystallographic Directions
z
Algorithm
1. Vector repositioned (if necessary) to pass
through origin.
a2 2. Read off projections in terms of unit
cell dimensions a1, a2, a3, or c
- 3. Adjust to smallest integer values
a3
4. Enclose in square brackets, no commas
a2
a1 [uvtw]
Adapted from Fig. 3.24(a),
Callister & Rethwisch 3e. a2 -a3
2
Chapter 3 - 47
Crystallographic Planes
• Algorithm
1. Read off intercepts of plane with axes in
terms of a, b, c
2. Take reciprocals of intercepts
3. Reduce to smallest integer values
4. Enclose in parentheses, no
commas i.e., (hkl)
Chapter 3 - 49
Crystallographic Planes
z
example a b c
1. Intercepts 1 1 c
2. Reciprocals 1/1 1/1 1/
1 1 0
3. Reduction 1 1 0 y
a b
4. Miller Indices (110)
x
z
example a b c
1. Intercepts 1/2 c
2. Reciprocals 1/½ 1/ 1/
2 0 0
3. Reduction 2 0 0
y
4. Miller Indices (100) a b
x
Chapter 3 - 50
Crystallographic Planes
z
example a b c c
1. Intercepts 1/2 1 3/4
2. Reciprocals 1/½ 1/1 1/¾
2 1 4/3 y
3. Reduction 6 3 4 a b
example a1 a2 a3 c
1. Intercepts 1 -1 1
2. Reciprocals 1 1/ -1 1
1 0 -1 1 a2
3. Reduction 1 0 -1 1
a3
Chapter 3 - 52
Crystallographic Planes
• We want to examine the atomic packing of
crystallographic planes
• Iron foil can be used as a catalyst. The
atomic packing of the exposed planes is
important.
a) Draw (100) and (111) crystallographic planes
for Fe.
b) Calculate the planar density for each of these
planes.
Chapter 3 - 53
Planar Density of (100) Iron
Solution: At T < 912C iron has the BCC structure.
2D repeat unit
(100) 4 3
a R
3
Adapted from Fig. 3.2(c), Callister & Rethwisch 3e. Radius of iron R = 0.1241 nm
atoms
2D repeat unit 1
1 atoms atoms
Planar Density = = 2 = 12.1 = 1.2 x 10 19
area a2 4 3 nm 2
m2
R
2D repeat unit 3
Chapter 3 - 54
Planar Density of (111) Iron
Solution (cont): (111) plane 1 atom in plane/ unit surface cell
2a atoms in plane
atoms above plane
nit
atoms below plane
tu
ea
r ep
3
h a
2D 2
2
4 3 16 3 2
area 2 ah 3 a 3 2
R R
atoms 3 3
2D repeat unit 1
atoms = atoms
Planar Density = = 7.0 0.70 x 1019
area 16 3 2
nm
2
m2
R
2D repeat unit 3
Chapter 3 - 55
X-Ray Diffraction
”
r
“1
in ray
co s
ys
X- reflections must
m
ra be in phase for
X-
in
”
“2
g
a detectable signal
“1
ng
”
extra
o i
“2
g Adapted from Fig. 3.37,
distance
ut
”
o Callister & Rethwisch 3e.
travelled
by wave “2” spacing
d between
planes
Measurement of X-ray
intensity n
critical angle, c, d
(from 2 sin c
allows computation of
detector)
planar spacing, d.
c
Chapter 3 - 57
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
Chapter 3 - 58
SUMMARY
• Atoms may assemble into crystalline or amorphous structures.
• 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.
• Crystallographic points, directions and planes are specified in
terms of indexing schemes. Crystallographic directions and
planes are related to atomic linear densities and planar densities.
Chapter 3 - 59
SUMMARY
Chapter 3 - 60
ANNOUNCEMENTS
Reading:
Core Problems:
Self-help Problems:
Chapter 3 - 61