Ch3-Metal and Ceramic Structures
Ch3-Metal and Ceramic Structures
Ch3-Metal and Ceramic Structures
Structures
The properties of some materials are
directly related to their crystal
structures.
Significant property differences exist
between crystalline and noncrystalline
materials having the same composition.
Energy
typical neighbor
bond length
typical neighbor
bond energy
r
Energy
typical neighbor
bond length
typical neighbor
bond energy
Noncrystalline materials...
atoms have no periodic packing
occurs for: -complex structures
-rapid cooling
"Amorphous" = Noncrystalline
crystalline SiO2
Si
Oxygen
noncrystalline SiO2
4
vs.
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
8
Coordination # = 8
2 atoms/unit cell: 1 center + 8 corners x 1/8
9
a
2a
Close-packed directions:
length = 4R = 3 a
atoms
volume
4
( 3a/4) 3
2
unit cell
atom
3
APF =
volume
a3
unit cell
10
Coordination # = 12
4 atoms/unit cell: 6 face x 1/2 + 8 corners x 1/8
11
2a
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
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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
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X-Ray Diffraction
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X-Ray Diffractometer
Detector
Xray-Tube
Xray-Tube
le
p
m
a
s
Sample
Metal Target
(Cu or Co)
Detector
Braggs Equation
d = /2 sin
Theoretical Density,
Density = =
=
where
nA
VC NA
Theoretical Density,
Ex: Cr (BCC)
A (atomic weight) = 52.00 g/mol
n = 2 atoms/unit cell
R = 0.125 nm
R
atoms
unit cell
=
volume
unit cell
a
2 52.00
a3 6.022 x 1023
a = 4R/ 3 = 0.2887 nm
g
mol
theoretical
= 7.18 g/cm3
actual
= 7.19 g/cm3
atoms
mol
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unstable
2. Maintenance of
Charge Neutrality:
stable
CaF 2 :
stable
Ca 2+ +
cation
Fanions
F-
A m Xp
m, p values to achieve charge neutrality
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r cation
Coordination # increases with r
anion
Coord
#
2
linear
0.155 - 0.225
0.225 - 0.414
4 tetrahedral
0.414 - 0.732
6 octahedral
0.732 - 1.0
triangular
cubic
ZnS
(zinc blende)
NaCl
(sodium
chloride)
CsCl
(cesium
chloride)
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2ranion 2rcation 2a
a 2ranion
(C.N. = 6)
rcation ( 2 1)ranion
rcation
2 1 0.414
ranion
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0.140
0.181
0.133
Answer:
rcation 0.077
ranion 0.140
0.550
based on this ratio,
-- coord # = 6 because
0.414 < 0.550 < 0.732
-- crystal structure is similar to NaCl
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rO = 0.140 nm
Mg2+
rMg = 0.072 nm
rMg/rO = 0.514
cations prefer octahedral sites
AX Crystal Structures
AXType Crystal Structures include NaCl, CsCl, and zinc blende
Cesium Chloride structure:
rCs
rCl
0.170
0.939
0.181
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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.
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