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ISSUES TO ADDRESS...
Structures of ceramic materials:
How do they differ from that of metals?
Define basic terms and give examples of each:
Lattice
Basis Atoms (Decorations or Motifs)
Crystal Structure
Unit Cell
Coordination Numbers
Describe hard-sphere packing and identify cell symmetry.
BondinginCeramics
Bonding:
--Mostly ionic, some covalent.
--% ionic character increases with difference in electronegativity.
Large vs small ionic bond character:
H
2.1
Li
1.0
CaF 2: large
He
-
C
2.5
Si
1.8
SiC: small
Be
1.5
F
4.0
Na
0.9
K
0.8
Rb
0.8
Ca
1.0
Sr
1.0
I
2.5
Cs
0.7
Ba
0.9
At
2.2
Fr
0.7
Ra
0.9
Mg
1.2
Ti
1.5
Cr
1.6
Fe
1.8
Ni
1.8
Zn
1.8
As
2.0
Cl
3.0
Br
2.8
Ne
Ar
Kr
Xe
Rn
-
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.
MSE 280: Introduction to Engineering Materials
IonicCrystals
Most ionic crystals can be considered as close-packed structure of BIG anions
with SMALL cations in the interstitial sites (spaces between BIG anions).
Table 3.2
TetrahedralandOctahedralHolesinClosePackedCrystals
See holes: stack pennies in either FCC or HCP and see interstitial sites.
Tetrahedral site
FCC
Octahedral site
MSE 280: Introduction to Engineering Materials
HCP
D.D. Johnson 2004, 2006-10
InterstitialsSitesinFCC
Octahedral (Oh) sites
1 at the center
12 edge sites
(each shared by 4 cells)
InterstitialsSitesinHCP
Looking down [0001] of HCP unit cell
3 Oh sites on top half of unit cell (by symmetry, 3 more on bottom half)
6 Td sites on top half of unit cell (by symmetry, 6 more on bottom half)
Total 6 Oh sites
MSE 280: Introduction to Engineering Materials
Total 12 Td sites
D.D. Johnson 2004, 2006-10
InterstitialsSitesinHCP
6 atoms in HCP unit cell = 12*(1/6) + 3 + 2*(1/2)
corners interior faces
Total 6 Oh sites
Total 12 Td sites
IonicStructures:FillingintheholesbetweenAnions
Charge Neutrality:
CaF 2:
Ca2+ +
cation
Fanions
F-
Stable structures:
unstable
stable
stable
D.D. Johnson 2004, 2006-10
10
CoordinationNumberandIonicRadii
Coordination # increases with
Issue: How many anions can you arrange around a cation?
Table 3.3 text
rcation
ranion
< .155
Coord #
2
.155-.225 3
.225-.414 4
.414-.732 6
.732-1.0
ZnS
(zincblende)
Adapted from Fig. 12.4,
Callister 6e.
NaCl
(sodium
chloride)
CsCl
(cesium
chloride)
11
CoordinationNumberandIonicRadii
How does geometry determine this?
Negative electron
density overlaps
strongly so unstable
Fig. 3.4
AP
rA
AO r A rC
rC 1 3/2
0.155
rA
3/2
From Fig. 3.4, show that 6-atom coordinated gives rC/rA = 0.414.
MSE 280: Introduction to Engineering Materials
12
3DGeometry:LimitingCation/AnionRation
13
ExamplePredictingAXstructures
Using neutrality and ionic radii, what structure is predicted?
Step 1: Check Valence (Zn2+ and S2-) and Charge Neutrality
Zn2+ : S2- = 1:1 to get Formula Unit ZnS
Consider ZnS:
From Table 3.4
r Zn 0.074nm
rS
0.184nm
0.402
14
ExampleEXAMQUESTIONS
The zinc blende crystal structure is one that may be generated from closepacked planes of anions.
(a) Will the stacking sequence be FCC or HCP? Why?
(b) Will cations fill tetrahedral or octahedral sites? Why?
(c) What fraction of the positions will be occupied?
This question is concerned with the zinc blende crystal structure in terms of
close-packed planes of anions. (See previous slide.)
(a) The stacking sequence of close-packed planes of anions for the zinc
blende crystal structure will be the same as FCC (and not HCP)
because the anion packing is FCC (Table 3.5).
(b) The cations will fill tetrahedral positions since the coordination number
for cations is 4 (Table 3.5).
(c) Only one-half of the tetrahedral positions will be occupied because there
are two tetrahedral sites per anion, and yet only one cation per anion.
15
ExampleofAXstructures:SodiumChloride
Using neutrality ionic radii, what structure is predicted?
From Valence (Na+ and Cl-) and Charge Neutrality,
#Na+ ions : # Cl- ions is 1:1, so NaCl is formula unit.
Consider NaCl :
From Table 3.4
rNa 0.102nm
rCl 0.181nm
0.564
16
SodiumChlorideStructuresObservedasCubes
17
ExampleofAXstructures:CesiumChloride
Using neutrality and ionic radii, what structure is predicted?
From Valence (Cs+ and Cl-) and Charge Neutrality,
Cs+ : Cl- = 1:1, and CsCl is formula unit.
Consider CsCl :
From Table 3.4
rCs 0.170nm
rCl
0.181nm
0.939
18
ExampleofAX2:StructureofCalciumFluoride
Using neutrality and ionic radii, what structure is predicted?
From Valence (Ca2+ and F-) and Charge Neutrality,
Ca2+ : F- = 1:2, so CaF2 is formula unit.
Consider CaF2 :
From Table 3.4
rC 0.100nm
r A 0.133nm
0.752
19
Notesamestructurescanappeardifferently
CaF2withratioof1:2forchargeneutrality
Based solely on rCa/rF= 0.752, the coord. no. is CN=8 for Ca2+.
Option 1
Connect F
(anions)
Ca2+
With CN=8 for Ca2+ , and for AX2 where Ca:F is 1:2, F
must have CN= 8/2 = 4 (or tetrahedral coordination)
with Ca. (Careful, this does not always work, e.g.
ABX3.)
Connect Ca
(cations)
20
SynopsisofStructuresFoundFillingHoles
21
(vacuum level)
2s
1s2
2p5
2s
Li
1s2
Z1Z 2e 2
EC
4 0r
D.D. Johnson 2004, 2006-10
22
(cont.)IdealIONICBONDSMadelungEnergy
Coulomb Energy between 2 point
charges distance r apart:
3r
Z1Z 2e2
EC
r
6r
2r
5r
Z1Z 2e2
EC
40r
CGS
SI
2r
12e 2
6e 2
E
2r
r
e2
2
8e 2
24e 2
6e 2 24e
3r
5r
6r
2r
12
8
6
e2
... M
6
r
2
3 2
Madelung Constant
(depends on crystal structure but not on atomic composition)
MSE 280: Introduction to Engineering Materials
23
(cont.)IdealIONICBONDS
Only attractive term: crystal will collapse on itself. Real ions are not point charges!
e2
e2
E M
B
r
rn
2
n1
dr r r
ro
ro
o
So, B
Me2
1
E r ro
1
ro
n
MN0Z1Z2e2
1
U
1
ro
n
In general
(molar
lattice
energy): to Engineering Materials
MSE
280: Introduction
M n1
ro
n
Er r
Me2
1
40ro
n
MN0 Z1Z2e2
1
U
1
40ro
n
24
(cont.)CompareSystems
Both NaCl and MgO have rock salt structure (M = 1.748)
Given:
ro
NaCl
0.282nm
9.1
MgO
0.210nm
5.4
25
26
ExampleofAmBnXpStructures
1. ABX3 Type (e.g. Calcium titanate CaTiO3) Perovskite structure
1 Ti4+ at the center
8 Ca2+ at the corners (effectively 1/unit cell)
6 O2- on the faces (effectively 3/unit cell)
27
ExampleofAmBnXpStructures
2. AB2X4 Type (e.g. Lanthinum Copper Oxide or CuLa2O4)
28
ExampleofAmBnXpStructures
2. AB2X4 Type (e.g. Magnesium Aluminate or spinel MgAl2O4) Spinel structure
FCC of O2 Mg2+ in tetrahedral sites (1/8 filled)
Al3+ in octahedral sites (half filled)
The mineral Spinel Mg2+Al23+O42- is obtained by placing O2- on an FCC lattice and
filling SOME tetrahedral sites with Mg2+ and filling some octahedral sites with
Al3+.
The complete unit cell requires 32 O, 16 Al, and 8 Mg atoms to define it.
Partial
Unit Cell
29
CalculatingDENSITY
nC = number of cations in unit cell
AC = atomic weight of cation
nA = number of anions in unit cell
AA = atomic weight of anion
V = volume of unit cell
No = Avogadros number
Simple AB structures:
nC AC n A AA
N oV
In general:
j n j Aj
N oV
Ask yourself
What is its formula unit?
How many formula units?
How is a related to rC and rA?
What is volume of cell?
30
ExampleofSilicateCeramics
Primarily composed of Si and O
Charge neutrality:
Radii ratio:
RSi 4
RO 2
Si4+:O2-=1:2
0.040nm
0.286
0.140nm
SiO2
Coordination # = 4
(tetrahedral)
However:
% ionic character = 51%
(relatively small ionic character
significant covalent character exists)
What structure(s) do we expect?
31
CrystallineSilica
32
BuildingBlocksofSilica
Single Chains of
(SiO4)4 tetrahedra
Double Chains of
(SiO4)4 tetrahedra
33
SheetsofSilica
34
KaoliniteClay
Al2(OH)42+ Layer
Layer
plus a (Si2O5)2-
35
FormationofCommonGlasses
36
SilicateGlasses
Sodium-silicate glass
Amorphous silica forms a network with
relatively large open areas where foreign
atoms and particles may be easily introduced.
Silicates: amorphous silica with impurities
37
SilicateGlasses
2D Silicate sheets
(Si2O5)2
38
CrystallineandNonCrystallineSilica
39
CarbonBased
40
Diamond
41
RECALL:hybridorbitalsareresponsible.
Atomic Orbitals
an s-orbital
px
py
pz
y
x
Hybridization
1 x s + 1 x p = sp-orbitals
1 x s + 2 x p = sp2-orbitals
60
y
y
x
1 x s + 3 x p = sp3-orbitals
60
x
42
43
CarbonNanotubes
C60: Buckey Ball
44
CarbonNanotubes
45
CarbonMultiwallNanotubes
46
MetallicCarbonNanotubes
(10, 0) SWNT
graphene
ZIGZAG
Semiconducting
47
MetallicCarbonNanotubes
graphene
48
MetallicCarbonNanotubes
CHIRAL
Semiconducting
49
How to predict:
Interstitial sites (its just geometry!)
Ionic radii ratios (its just geometry!)
Structures (its mostly valence and RC/RA)
Lattice energy (its mostly Madelung energy)
Silica & silicates. (valence and bonds)
Carbon (diamond, graphite, fullerenes).
50