STRUCTURE OF SOLIDS

Types of solids based on structure

Types of solids based on bonding
UNIVERSE
PARTICLES
ENERGY
SPACE
FIELDS
STRONG
WEAK
ELECTROMAGNETIC
GRAVITY
METAL
SEMI-METAL
SEMI-CONDUCTOR
INSULATOR
nD + t
HYPERBOLIC
EUCLIDEAN
SPHERICAL
GAS
BAND STRUCTURE
AMORPHOUS
ATOMIC
NON-ATOMIC
STATE / VISCOSITY
SOLID LIQUID
LIQUID
CRYSTALS
QUASICRYSTALS
CRYSTALS
RATIONAL
APPROXIMANTS
STRUCTURE
NANO-QUASICRYSTALS NANOCRYSTALS
SIZE
AMORPHOUS
CLASSIFICATION OF SOLIDS BASED ON ATOMIC
ARRANGEMENT
QUASICRYSTALS CRYSTALS
Ordered
+
Periodic
Ordered
+
Periodic
Ordered
+
Periodic
There exists at least one crystalline state of lower energy (G) than
the amorphous state (glass)
The crystal exhibits a sharp melting point
Crystal has a higher density!!
AMORPHOUS
CLASSIFICATION OF SOLIDS BASED ON ATOMIC
ARRANGEMENT
QUASICRYSTALS CRYSTALS
ADDITIONAL POSSIBLE STRUCTURES
Modulated structures
Incommensurately
Modulated structures
Liquid crystals
THE ENTITY IN QUESTION
GEOMETRICAL PHYSICAL
E.g. Atoms, Cluster of Atoms
Ions, etc.
E.g. Electronic Spin, Nuclear spin
ORDER
ORIENTATIONAL
POSITIONAL
ORDER
TRUE
PROBABILISTIC
Order-disorder of: POSITION, ORIENTATION, ELECTRONIC & NUCLEAR SPIN
ORIENTATIONAL
POSITIONAL
PROBABILISTIC
OCCUPATION
Perfect
Average
Perfect
Average
Positionally ordered
Probabilistically ordered
A B
Probability of
occupation:
A 50%
B 50%
Order
Spatial Temporal
Range of Spatial Order
Short Range (SRO) Long Range Order (LRO)
Class/
example(s) +
Short Range Long Range
Ordered Disordered Ordered Disordered
Crystals
*
/
Quasicrystals

Glasses
#

Crystallized
virus
$


Gases
Notes:
* In practical terms crystals are disordered both in the short range (thermal vibrations) and
in the long range (as they are finite)
# ~ Amorphous solids
$ Other examples could be: colloidal crystals, artificially created macroscopic crystals
Liquids have short range spatial order but NO temporal order
Crystal Physics, G.S. Zhdanov, Oliver & Boyd, Ediburgh, 1965
When primary bonds are 1D or 2D and secondary bonds aid in the
formation of the crystal
The crystal structure is very complex
Factors affecting the formation of the amorphous state
When the free energy difference between the crystal and the glass is
small Tendency to crystallize would be small
Cooling rate fast cooling promotes amorphization
- fast depends on the material in consideration
- Certain alloys have to be cooled at 10
6
K/s for amorphization
- Silicates amorphizes during air cooling
COVALENT
CLASSIFICATION OF SOLIDS BASED ON BONDING
IONIC
METALLIC
Molecular
CRYSTALS
Non-molecular
COVALENT
IONIC
METALLIC
Molecule held together by primary
covalent bonds
Intermolecular bonding is Van der walls
Bond Type kJ/mol
Covalent Bond 250
Electrostatic 5
van der Waals 5
Hydrogen bond

20
Approximate Strengths of Interactions
between atoms
METALLIC
Positive ions in a free electron cloud
Metallic bonds are non-directional
Each atoms tends to surround itself with as many neighbours as possible!
Usually high temperature (wrt to MP) BCC (Open structure)
The partial covalent character of transition metals is a possible reason
for many of them having the BCC structure at low temperatures
FCC Al, Fe (910 - 1410C), Cu, Ag, Au, Ni, Pd, Pt
BCC Li, Na, K , Ti, Zr, Hf, Nb, Ta, Cr, Mo, W, Fe (below 910C),
HCP Be, Mg, Ti, Zr, Hf, Zn, Cd
Others La, Sm Po, -Mn, Pu
CLOSE PACKING
A B C
+ +
FCC
=
Note: Atoms are coloured differently but are the same
FCC
A
B
+
HCP
=
A
+
Note: Atoms are coloured differently but are the same
HCP
Shown displaced for clarity
Unit cell of HCP (Rhombic prism)
Note: diagrams not to scale
Atoms: (0,0,0), (, ,)
a CV
4
6
=
a CV
12
6
=
a VC CF h
3
2
= + =
632 . 1
3
2
2
2
= = =
a
h
a
c
IDEAL c/a
h
PACKING FRACTION / Efficiency
Cell of Volume
atoms by occupied Volume
Fraction Packing =
SC
*
BCC
*
CCP DC HCP
Relation between atomic radius (r)
and lattice parameter (a)
a = 2r a = 2r


Atoms / cell 1 2 4 8 2
Lattice points / cell 1 2 4 4 1
No. of nearest neighbours 6 8 12 4 12
Packing fraction

= 0.52 = 0.68 = 0.74 = 0.34 = 0.74
r a 4 3 =
r a 4 2 = r a 2
4
3
=
6
t
8
3t
6
2t
16
3t
3
2
4r c =
6
2t
* Crystal formed by monoatomic decoration of the lattice
ATOMIC DENSITY (atoms/unit area)
SC FCC BCC
(100) 1/a
2
= 1/a
2
2/a
2
= 2/a
2
1/a
2
= 1/a
2
(110) 1/(a
2
\2) = 0.707/a
2
\2/a
2
= 1.414/a
2
\2/a
2
= 1.414/a
2
(111) 1/(\3a
2
) = 0.577/a
2
4/(\3a
2
) = 2.309/a
2
1/(\3a
2
) = 0.577/a
2
Order (111) < (110) < (100) (110) < (100) < (111) (111) < (100) < (110)
FCC
BCC
(100)
(110)
(111)
SC
a
a 2
a 2
a 2
a 2
a
a
a
a 2
a 2
ATOMIC DENSITY (area covered by atoms/unit area)
SC FCC BCC
Atoms /
Area
Area / Area Atoms /
Area
Area / Area Atoms /
Area
Area / Area
(100) 1/a
2


t/4 = 0.785 2/a
2


t/4 = 0.785 1/a
2
3t/16 =
0.589
(110) \2/(2a
2
)

0.707(t/4) =
0.555
\2/a
2


\2t/8 = 0.555 \2/a
2
3\2t/16 =
0.833
(111) 1/(\3a
2
)

0.577(t/4) =
0.453
4/(\3a
2
)

t/(2\3) =0.9068 1/(\3a
2
)

\3t/16 =
0.34
VOIDS
TETRAHEDRAL
OCTAHEDRAL
FCC
Note: Atoms are coloured differently but are the same
cell n tetrahedro
V V
24
1
=
cell octahedron
V V
6
1
=
way along body diagonal
{, , }, {, , }
+ face centering translations
At body centre
{, , }
+ face centering translations
FCC- OCTAHEDRAL
{, , } + {, , 0} = {1, 1, } {0, 0, }
Face centering translation
Note: Atoms are coloured differently but are the same
Equivalent site for an
octahedral void
Site for octahedral void
FCC voids Position Voids / cell Voids / atom
Tetrahedral
way from each vertex of the cube
along body diagonal <111>
((, , ))
8 2
Octahedral
Body centre: 1 (, , )
Edge centre: (12/4 = 3) (, 0, 0)
4 1
Size of the largest atom which can fit into the tetrahedral void of FCC
CV = r + x
Radius of the
new atom
e
x r e + =
4
6
225 . 0 ~ 1
2
3
2
|
|
.
|

\
|
= =
r
x
r e
Size of the largest atom which can fit into the Octahedral void of FCC
2r + 2x = a
r a 4 2 =
( ) 414 . 0 ~ 1 2 =
r
x
VOIDS
TETRAHEDRAL
OCTAHEDRAL
HCP
These voids are identical to the ones found in FCC
Note: Atoms are coloured differently but are the same
Coordinates: ( ,), (,,)
) , , ( ), , , ( ), , 0 , 0 ( ), , 0 , 0 ( :
8
7
3
1
3
2
8
1
3
1
3
2
8
5
8
3
s Coordinate
Octahedral voids occur in 1 orientation, tetrahedral voids occur in 2 orientations
The other orientation of the tetrahedral void
Note: Atoms are coloured differently but are the same
Note: Atoms are coloured differently but are the same
Note: Atoms are coloured differently but are the same
Octahedral voids
Tetrahedral void
HCP voids Position
Voids /
cell
Voids / atom
Tetrahedral
(0,0,3/8), (0,0,5/8), (, ,1/8),
(,,7/8)
4 2
Octahedral ( ,), (,,) 2 1
Voids/atom: FCC HCP
as we can go from FCC to HCP (and vice-
versa) by a twist of 60 around a central atom of
two void layers (with axis to figure)
Central atom
Check below
Atoms in HCP crystal: (0,0,0), (, ,)
A
A
B
VOIDS
Distorted TETRAHEDRAL
Distorted OCTAHEDRAL
**

BCC
a
a\3/2
a
a\3/2
r
void
/ r
atom
= 0.29
r
Void
/ r
atom
= 0.155
Note: Atoms are coloured differently but are the same
** Actually an atom of correct size touches only
the top and bottom atoms
Coordinates of the void:
{, 0, } (four on each face)
Coordinates of the void:
{, , 0} (+ BCC translations: {0, 0, })
Illustration on one face only
BCC voids Position
Voids /
cell
Voids /
atom
Distorted
Tetrahedral
Four on each face: [(4/2) 6 = 12] (0, , ) 12 6
Distorted
Octahedral
Face centre: (6/2 = 3) (, , 0)
Edge centre: (12/4 = 3) (, 0, 0)
6 3
{0, 0, })
From the right angled triange OCM:
4 16
2 2
a a
OC + =
5
4
a r x = = +
For a BCC structure: 3 4 a r = (
3
4r
a = )
x r
r
+ =
3
4
4
5
29 . 0 1
3
5
=
|
|
.
|

\
|
=
r
x

a
a\3/2
BCC: Distorted Tetrahedral Void
2
a
x r OB = + =
3 2
4r
x r = +
r a BCC 4 3 : =
1547 . 0 1
3
3 2
=
|
|
.
|

\
|
=
r
x
Distorted Octahedral Void
a\3/2
a
a
a
OB 5 . 0
2
= =
a
a
OA 707 .
2
2
= =
As the distance OA > OB the atom in the void
touches only the atom at B (body centre).
void is actually a linear void
This implies:

A 292 . 1 =
Fe
FCC
r

A 534 . 0 ) ( = oct x
Fe
FCC

A 77 . 0 =
C
r
C
N
Void (Oct)




Fe
FCC

O

A 258 . 1 =
Fe
BCC
r

A 364 . 0 ) . ( = tet d x
Fe
BCC

A 195 . 0 ) . ( = oct d x
Fe
BCC
FCC
BCC
Fe
BCC

Relative sizes of voids w.r.t to atoms
( . )
0.155
Fe
BCC
Fe
BCC
x d oct
r
=
( . )
0.29
Fe
BCC
Fe
BCC
x d tet
r
=

A 258 . 1 =
Fe
BCC
r
2
2
A
a
OA r x = + =
2 6
3
A
r
r x + =
r a BCC 4 3 : =
2 6
1 0.6329
3
A
x
r
| |
= =
|
|
\ .
Ignoring the atom sitting at B and assuming the interstitial atom touches the atom at A
0.796A
A
OX x = = 0.195A
B
OY x = =

A 364 . 0 ) . ( = tet d x
Fe
BCC
r
void
/ r
atom

SC BCC FCC DC
Octahedral
(CN = 6)
0.155
(distorted)
0.414 -
Tetrahedral
(CN = 4)
0.29
(distorted)
0.225
1
(,,) & (, , )
Cubic
(CN = 8)
0.732
Summary of void sizes
The primitive UC for the FCC lattice is a Rhombohedron
Primitive unit cell made of 2T + 1O
Occupies the volume of the cell
FCC
Note: Atoms are coloured differently but are the same
ADDITION OF ALLOYING ELEMENTS
Element Added
Segregation / phase separation
Solid solution
Compound /Intermediate structure
(new crystal structure)
Interstitial
Substitutional
Ordered
1
2
3
Segregation / phase separation
The added element does not dissolve in the parent/matrix phase
in a polycrystal may go to the grain boundary
1
Chemical
compounds
Valency compounds (usual)
Electrochemical compounds : Zintl
Mg
2
Sn, Mg
2
Pb, MgS etc.
Interstitial Phases: Hagg
Determined by R
x
/ R
M
ratio
W
2
C, VC, Fe
4
N etc.
Electron compounds
specific e/a ratio [21/14, 21/13, 21/12]
CuZn, Fe
5
Zn
21
, Au
3
Sn
Etc.
3
Size Factor compounds
Laves phases, Frank-Kasper Phases
Chemical compounds
Different crystal lattice as compared to the components
Each component has a specific location in the lattice
A
n
B
m

Different properties than components
Constant melting point and dissociation temperature
Accompanied by substantial thermal effect
Zintl Phases:
Electrochemical compounds
Solid solution
Interstitial Substitutional
The mixing is at the atomic scale and is analogous to a liquid solution

NOTE
Pure components A, B, C
Solid solutions o, |,
Ordered Solid solutions o, |,
2
Substitutional Solid Solution
HUME ROTHERY RULES
Empirical rules for the formation of substitutional solid solution
The solute and solvent atoms do not differ by more than 15% in diameter
The electronegativity difference between the elements is small
The valency and crystal structure of the elements is same

Additional rule

Element with higher valency is dissolved more in an element of lower
valency rather than vice-versa
System
Crystal
structure
Radius of
atoms ()
Valency Electronegativity
Ag-Au
Ag FCC 1.44 1 1.9
Au FCC 1.44 1 2.4
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
Examples of pairs of elements satisfying Hume Rothery rules and forming
complete solid solution in all proportions
A continuous series of solid solutions may not form even if the above
conditions are satisfied e.g. Cu- Fe
Counter example of a pair of elements not forming solid solution in all
proportions
Cu
Zn
FCC
Valency 1
HCP
Valency 2
35% Zn in Cu
1% Cu
in Zn
Ordered Solid solution
G = H TS
High T disordered
Low T ordered
470C
Sublattice-1
Sublattice-2
BCC
SC
In a strict sense this is not a crystal !!
ORDERING
A-B bonds are preferred to AA or BB bonds
e.g. Cu-Zn bonds are preferred compared to Cu-Cu or Zn-Zn bonds
The ordered alloy in the Cu-Zn alloys is an example of an
INTERMEDIATE STRUCTURE that forms in the system with
limited solid solubility
The structure of the ordered alloy is different from that of both the
component elements (Cu-FCC, Zn-HCP)
The formation of the ordered structure is accompanied by change in
properties. E.g. in Permalloy ordering leads to reduction in
magnetic permeability, increase in hardness etc. [~Compound]
Complete solid solutions are formed when the ratios of the components
of the alloy (atomic) are whole no.s 1:1, 1:2, 1:3 etc.
[CuAu, Cu
3
Au..]
Ordered solid solutions are in-between solid solutions and chemical
compounds
Degree of order decreases on heating and vanishes on reaching
disordering temperature [= compound]
Interstitial Solid Solution
The second species added goes into the voids of the parent lattice
Octahedral and tetrahedral voids
E.g. C (r = 0.77 ), N (r = 0.71 ), H (r = 0.46 )