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Chapter 5
Structure of
Solids
6 Lectures
2
Solids
Crystalline Noncrystalline
Gives sharp
diffraction patterns
Does not give sharp
diffraction patterns
Long-range periodicity No long-range periodicity
Has sharp melting point
Does not have a sharp
meliing point
Has higher density
Has a lower density
3
4
Factors promoting the formation of noncrystalline
structures
1. Primary bonds do not extend in all three
directions and the secondary bonds are not
strong enough.
2. The difference in the free energy of the
crystalline and non crystalline phases is small.
3. The rate of cooling from the liquid state is
higher than a critical cooling rate.
Metallic Glass: 10
6
K s
-1
5
Inorganic Solids
Covalent Solids
Metals and Alloys
Ionic Solids
Silica: crystalline and amorphous
Polymers
Classification
Structure
Crystallinity
Mechanical Behaviour
6
7
th
. Group (Halogens): single covalent bonds
Diatomic molecules
Weak van der Waals bond between molecules
F
2
, Cl
2
: Gas; Br
2
: Liquid;
I
2
: orthorhombic xl
7
6
th
. Group: two covalent bonds: long zig-zag chains
Weak van der Waals bonds between chains
mostly noncrystalline
8
5
th
. Group: Three covalent bonds: Puckered sheets
Weak van der Waals bond between sheets
Mostly noncrystalline
9
4
th
. Group: Carbon
10
Graphite
Diamond
Buckminster Fullerene
1985
Carbon Nanotubes
1991
Graphene
2004
Allotropes of C
11
Graphite
Sp
2
hybridization 3 covalent bonds
Hexagonal sheets
x
y
a
b=a
=120
a = 2 d cos 30
= 3 d
d = 1.42
a = 2.46
12
Graphite
x
y
a = 2.46
c = 6.70
B
A
A
www.scifun.ed.ac.uk/
c
Lattice: Simple Hexagonal
Motif: 4 carbon atoms
13
Graphite
Highly Anisotropic:
Properties are very different in the a and c directions
www.sciencemuseum.org.uk/
Uses:
Solid lubricant
Pencils (clay + graphite, hardness
depends on fraction of clay)
carbon fibre
14
Diamond
Sp
3
hybridization 4 covalent bonds
Location of atoms:
8 Corners
6 face centres
4 one on each of the 4 body diagonals
Tetrahedral bonding
15
Diamond Cubic Crystal: Lattice & motif?
A
A B
B
C
C D
D
x
y
P
P
Q
Q
R
R
S
S
T
T
K
K
L
L
M
M
N
N
0,1
0,1
0,1
0,1
0,1
4
1
4
1
4
3
4
3
Diamond Cubic Crystal
= FCC lattice + motif:
x
y
2
1
2
1
2
1
2
1
Projection of the unit cell on
the bottom face of the cube
000;
16
Crystal Structure = Lattice + Motif
Diamond Cubic
Crystal Structure
FCC
Lattice
2 atom
Motif

'

4
1
4
1
4
1
000
= +
There are only three Bravais Lattices: SC, BCC, FCC.
Diamond Cubic
Lattice
17
There is no
diamond
cubic
lattice.
18
Diamond Cubic
Structure
Effective number of atoms in the unit cell =
8
8
1

Corners
Relaton between lattice parameter
and atomic radius
r
a
2
4
3

3
8r
a
Packing efficiency
34 . 0
16
3
3
4
8
3
3

a
r
Coordination
number
4
8 6
2
1
+ 4 1 +
Inside Face
19
Diamond Cubic Crystal Structures
C Si Ge Gray Sn
a () 3.57 5.43 5.65 6.46
20
0,1
0,1
2
1
IV-IV compound: SiC
III-V compound:
AlP, AlAs, AlSb,
GaP, GaAs, GaSb,
InP, InAs, InSb
II-VI compound:
ZnO, ZnS,
CdS, CdSe, CdTe
I-VII compound:
CuCl, AgI
y
S
0,1 0,1
0,1
4
1
4
1
4
3
4
3
2
1
2
1
2
1
Equiatomic binary AB compounds having
diamond cubic
like structure
21
USES:
Diamond
Abrasive in polishing and grinding
wire drawing dies
Si, Ge, compounds:
semiconducting devices
SiC
abrasives, heating elements of furnaces
22
Inorganic Solids
Covalent Solids
Metals and Alloys
Ionic Solids
Silica: crystalline and amorphous
Polymers
Classification
Structure
Crystallinity
Mechanical Behaviour
23
Metals and Alloys
As many bonds as geometrically possible (to
lower the energy)
2. Atoms as hard sphere (Assumption)
1, 2 & 3 Elemental metal crystals:
close packing of equal hard spheres
1. Metallic bond: Nondrectional (Fact)
Close packing
3. Elements (identical atoms)
24
Close packing of equal hard spheres
Arrangement of equal nonoverlapping spheres
to fill space as densely as possible
Sphere packing problem:
What is the densest packing of spheres in 3D?
Kissing Number Problem
Keplers conjecture, 1611 74 . 0
2 3
.

E P
What is the maximum number of spheres that
can touch a given sphere?
Coding Theory
Internet data transmission
25
Close packing of equal hard spheres
1-D packing
A chain of spheres
P.E.= Kissing Number=
Close-packed direction of atoms
=1 2
length total
length occupied
26
Close packing of equal hard spheres
2-D packing
A hexagonal layer of atoms
P.E.=
Kissing Number=6
Close-packed plane of atoms
Close-packed directions? 3
area total
area occupied
907 .
3 2


1940 L. Fejes Toth: Densest packing of circles in plane
27
Close packing of equal hard spheres
3-D packing
A
A
A
A A A A
A A
A
A
A A A
A
A
B B B
B B B
B B B
C
C
C
C
C
C C
C C
First layer A
Second layer B
Third layer A or C
Close packed crystals:
ABABAB Hexagonal close packed (HCP)
ABCABC Cubic close packed (CCP)
28
Geometrical properties of ABAB stacking
A
A
A
A A A A
A A
A
A
A A A
A
A
B B
B B B
B B B
C C
C
C
C
C
C
C C
B
A and B do not have identical neighbours
Either A or B as lattice points, not both
a
b = a
=120
Unit cell: a rhombus based prism with a=b c; ==90, =120
A
A
B
B
c
The unit cell contains only one lattice point (simple) but two atoms (motif)
ABAB stacking = HCP crystal = Hexagonal P lattice + 2 atom motif 000
2/3 1/3 1/2
29
c/a ratio of an ideal HCP crystal
A
A
A
A A A A
A A
A
A
A A A
A
A
B B
B B B
B B B
C C
C
C
C
C
C
C C
B
A single B atom sitting on a base of three A atoms forms a regular
tetrahedron with edge length a = 2R
The same B atom also forms an inverted tetrahedron with three A atoms
sitting above it
A
A
B
B
c
c = 2 height of a tetrahedron of edge length a
a c
3
2 2

30
Geometrical properties of ABCABC stacking
A
A
A
A A A A
A A
A
A
A A A
A
A
B B B
B B B
B B B
C
C
C
C
C
C C
C C
B
A
C
B
A
C
All atoms are equivalent and their centres form
a lattice
Motif: single atom 000
ABCABC stacking
= CCP crystal
= FCC lattice + single atom motif 000
3 a
31
Geometrical properties of ABCABC stacking
B
A
C
B
A
C
All atoms are equivalent and their centres form
a lattice
Motif: single atom 000
ABCABC stacking
= CCP crystal
= FCC lattice + single atom motif 000
3 a
32
Geometrical properties of ABCABC stacking
B
A
C
B
A
C
All atoms are equivalent and their centres form
a lattice
Motif: single atom 000
A
A
A
A A A A
A A
A
A
A A A
A
A
B B B
B B B
B B B
C
C
C
C
C
C C
C C
ABCABC stacking
= CCP crystal
= FCC lattice + single atom motif 000
3 a
33
A
C
A
Body
diagonal
B
Close packed planes in the FCC unit cell of cubic close
packed crystal
Close packed planes: {1 1 1}
B
34
Stacking sequence?
ABA: HCP
35
36
http://www.tiem.utk.edu/~gross/bioed/webmodules/s
pherefig1.gif
Find the mistake in the following picture:
37
Crystal Coordination Packing
Structure number efficiency
Diamond cubic (DC) 4 0.32
Simple cubic (SC) 6 0.52
Body centred cubic 8 0.68
Face-centred cubic 12 0.74
Table 5.1
Coordination Number and Packing Efficiency
Empty spaces are distributed in various
voids
38
Voids in Close-Packed Crystals
A
A A
B
A
A A A
A
B
B B
C
TETRAHEDRAL VOID OCTAHEDRAL VOID
A
No. of atoms defining 4 6
the void
No. of voids per atom 2 1
Edge length of void 2 R 2 R
Size of the void 0.225 R 0.414 R
Experiment 2
39
Location of Voids in FCC Unit cell
C
C
40
Solid Solution
A single crystalline phase consisting of two or more elements is
called a solid solution.
Substitutional Solid solution
of Cu and Zn (FCC)
Interstitial solid solution of
C in Fe (BCC)
41
Hume-Rothery Rules for Extensive
Solid Solution (Unlimited solubility)
Interstitial solid solution
Substitutional solid solution
1. Structure factor
Crystal structure of the two elements should be
the same
2. Size factor:
Size of the two elements should not differ
by more than 15%
3. Electronegativity factor:
Electronegativity difference between the elements
should be small
4. Valency factor:
Valency of the two elements should be the same
42
TABLE 5.2
System Crystal Radius of Valency Electro-
structure atoms, negativity
Ag-Cu Ag FCC 1.44 1 1.9
Au FCC 1.44 1 1.9
Cu-Ni Cu FCC 1.28 1 1.9
Ni FCC 1.25 2 1.8
Ge-Si Ge DC 1.22 4 1.8
Si DC 1.18 4 1.8
All three systems exhibit complete solid solubility.
43
BRASS
Cu + Zn
FCC HCP
Limited Solubility:
Max solubility of Cu in Zn: 1 wt% Cu
Max Solubility of Zn in Cu: 35 wt% Zn
Unfavourable structure factor
44
Ordered and Random
Substitutional solid solution
Random Solid
Solution
Ordered Solid
Solution
45
Disordered solid solution of -Brass:
Corner and centre both have
50% proibability of being
occupied by Cu or Zn45
Ordered solid solution of -Brass:
Corners are always occupied
by Cu, centres always by Zn
470C
Above
470C
Below
470C
Ordered and random substitutional solid
solution
-Brass: (50 at% Zn, 50 at% Cu)
46
Intermediate Structures
Crystal structure of
Cu:
FCC
Crystal structure of Zn: HCP
Crystal structure of
random -brass:
BCC
Such phases that have a crystal structure different
from either of the two components are called
INTERMEDIATE STRUCURES
If an intermediate structure occurs only at a fixed
composition it is called an INTERMETALLIC
COMPOUND, e.g. Fe
3
C in steels.
47
IONIC SOLIDS
Cation radius: R
+

Anion radius: R
-
1. Cation and anion attract each other.
Usually
+
> R R
2. Cation and anion spheres touch each other
1, 2, 3 => Close packing of unequal spheres
3. Ionic bonds are non-directional
48
IONIC SOLIDS
Local packing geometry
1. Anions and cations considered as hard spheres
always touch each other.
2. Anions generally will not touch, but may be close
enough to be in contact with each other in a
limiting situation.
3. As many anions as possible surround a central cation
for the maximum reduction in electrostatic
energy.
49
Anions not touching the
central cation,
Anions touching each
other
Anions touching
the central
cation
Anions touching
Anions touching
central cation
Anions not touching
each other
155 . 0 <
a
c
R
R
155 . 0
a
c
R
R
155 . 0 >
a
c
R
R
unstable Critically stable stable
Effect of radius ratio
2 155 . 0 > < Ligancy
R
R
a
c
3 155 . 0 Ligancy
R
R
a
c
50
3 155 . 0 Ligancy
R
R
a
c
However, when tetrahedral coordination
with ligancy 4 becomes stable
225 . 0
a
c
R
R
Recall tetrahedral void in close-packed
structure.
Thus
3 225 . 0 155 . 0 < Ligancy
R
R
a
c
51
Table 5.3
Ligancy as a Function of Radius Ration
Ligancy Range of radius ratio Configuration
2 0.0 0.155 Linear
3 0.155 0.225 Triangular
4 0.225 0.414 Tetrahedral
6 0.414 0.732 Octahedral
8 0.732 1.0 Cubic
12 1.0 FCC or HCP
52
Example 1:
NaCl
cae2k.com
on Coordinati Octahedral
Ligancy
R
R
Cl
Na
6
732 . 0 54 . 0 414 . 0
54 . 0

< <

+
NaCl structure =FCC lattice + 2 atom motif: Cl
-
0 0 0
Na

0 0
53
a R R
Cl Na
+

2 2
"
NaCl structure
continued
CCP of Cl

with Na
+
in ALL octahedral voids
54
seas.upenn.edu
Example 2 : CsCl Structure

< <

+
1 91 . 0 732 . 0
91 . 0
Cl
Cs
R
R
Ligancy 8
Cubic coordination of Cl
-

around Cs
+

CsCl structure = SC lattice + 2 atom motif: Cl 000
Cs
a R R
Cl Cs
3 2 2 +
+
BCC
55
Example 3: CaF
2
(Fluorite or fluorospar)

+
732 . 0 73 . 0
73 . 0
2
F
Ca
R
R
Octahedral or cubic
coordination
Actually cubic coordination of
F

around Ca
2+
But the ratio of number of F

to Ca
2+
is 2:1
So only alternate cubes of F

are filled with Ca
2+
56
Simple cubic crystal of F

with Ca
2+
in alternate cube centres
Alternately, Ca
2+
at
FCC sites with F

in
ALL tetrahedral voids
CaF structure= FCC lattice + 3 atom motif
Ca
2+
000
F

- - -
57
Example 4: ZnS (Zinc blende or sphalerite)
on Coordinati Octahedral
Ligancy
R
R
S
Zn
6
732 . 0 48 . 0 414 . 0
48 . 0
2
2

< <

+
However, actual ligancy is 4
(TETRAHEDRAL
COORDINATION)
Explanation: nature of bond is more covalent than ionic
wikipedia
58
seas.upenn.edu
ZnS structure
CCP of S
2
with Zn
2+
in alternate tetrahedral voids
ZnS structure = FCC lattice + 2 atom motif S
2
0 0 0
Zn
2+

59
pixdaus.com
60
theoasisxpress.com
61
62
pixdaus.com
What is common to
1, glass of the window
2. sand of the beach, and
3. quartz of the watch?
63
Structure of SiO
2

< <

+
414 . 29 . 0 225 . 0
29 . 0
2
4
O
Si
R
R
Bond is 50% ionic and 50 % covalent
Tetrahedral coordination of
O
2
around Si
4+
Silicate
tetrahedron
64
4
+
2

4
Silicate tetrahedron electrically
unbalanced
O
2
need to be shared between two tetrahedra
65
1. O
2
need to be shared between two tetrahedra.
2. Si need to be as far apart as possible
Face sharing Edge sharing Corner sharing
Silicate tetrahedra share corners
66
2D representation of 3D periodically repeating pattern of
tetrahedra in crystalline SiO
2
. Note that alternate tetrahedra
are inverted
67
2 D representation of 3D random network of silicate
tetrahedra in the fused silica glass
68
Modification leads to breaking of primary bonds between
silicat tetrahedra.
+ Na
2
O =
Na
Na
Network Modification by addition of
Soda
69
2 D representation of 3D random network of silicate
tetrahedra in the fused silica glass
70
5.7 Structure of Long Chain
Polymers
Degree of
Polymerization:
No. of repeating
monomers in a chain
109.5
A
C
C
C
H
H
71
Freedom of rotation about each bond in space
leads to different conformations of C-C
backbone
109.5
72
73
5.8 Crystallinity in long chain polymers
Fig. 5.17: semicrystalline polymer
74
Factors affecting crystallinity of a long chain
polymer
1. Higher the degree of polymerization lower is
the degree of crystallization.
Longer chains get easily entagled
75
Branching
2. More is the branching less is the tendency to
crystallize
76
Tacticity
3. Isotactic and syndiotactic polymers can
crystallize but atactic cannot.
77
Copoymers: polymeric analog of solid
solutions
4. Block and random copolymers promote non
crystallinity.
78
Plasticizers
Low molecular weight additives
Impedes chains coming together
Reduces crystallization
79
Elastomer
Polymers with very extensive elastic deformation
Stress-strain relationship is non-linear
Example: Rubber
80
Liquid
natural
rubber
(latex)
being
collected
from the
rubber
tree
81
Isoprene molecule
commons.wikimedia.org
C=C-C=C
H H
H H
H
H
3
C
82
C C C C
H H
H H
H
CH
3
Isoprene
molecule
Polyisoprene
mer
C C C C
H H
H H H CH
3
Polymerization
Liquid
(Latex)
83
C C C C
H H
H H H CH
3
C C C C
H H
H H
H CH
3
+ 2S
Vulcanisation
Weak
van der
Waals
bond
84
C C C C
H H
H H H CH
3
C C C C
H H
H H
H CH
3
S
Vulcanisation
S

Cross-
links
85
Natural
rubber
Elastomer Ebonite
liquid Elastic
solid
Hard &
brittle
not
x-linked
lightly
x-linked
heavily
x-linked
Effect of cross-linking on polyisoprene
86
Charles Goodyear
December 29, 1800-July 1, 1860
Debt at the time of
death $200,000
Life should not be estimated
exclusively by the standard of dollars
and cents. I am not disposed to
complain that I have planted and
others have gathered the fruits. One
has cause to regret only when he
sows and no one reaps.
87
Another interesting property of
elastomers
Thermal behaviour
88
Tensile force
F
Elastomer
sample
Elastomer sample
under tension
Coiled chains
straight
chains
heat
Higher
entropy
Lower
entropy
Still
lower
entropy
Contracts on
heating
89
Elastomers have ve thermal
expansion coefficient, i.e., they
CONTRACT on heating!!
EXPERIMENT 4
Section 10.3 of the textbook
90
1
1
]
1

,
_

,
_

2
0
0 0
0
L
L
L
L
L
kT N
F
F applied tensile force
N
0
number of cross-links
k Boltzmann constant
T absolute temperature
L
0
initial length (without F)
L final length (with F)
91
Experimental
Theory: Chain uncoiling
1
1
]
1

,
_

,
_

2
0
0 0
0
L
L
L
L
L
kT N
F
Bond stretching in straightened
out molecules