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UNIVERSE
HYPERBOLIC
EUCLIDEAN
SPHERICAL
STRONG
WEAK
ELECTROMAGNETIC
ENERGY
SPACE
GRAVITY
nD + t
FIELDS
PARTICLES
METAL
SEMI-METAL
BAND STRUCTURE
NON-ATOMIC
ATOMIC
SEMI-CONDUCTOR
INSULATOR
STATE / VISCOSITY
GAS
SOLID
LIQUID
CRYSTALS
LIQUID
STRUCTURE
AMORPHOUS
QUASICRYSTALS
RATIONAL
APPROXIMANTS
CRYSTALS
SIZE
NANO-QUASICRYSTALS
NANOCRYSTALS
QUASICRYSTALS
Ordered
+
Periodic
CRYSTALS
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!!
QUASICRYSTALS
CRYSTALS
Modulated structures
Liquid crystals
GEOMETRICAL
PHYSICAL
ORDER
POSITIONAL
ORIENTATIONAL
ORDER
TRUE
PROBABILISTIC
ORIENTATIONAL
Perfect
Average
Perfect
POSITIONAL
Average
Positionally ordered
PROBABILISTIC
OCCUPATION
Probabilistically ordered
Probability of
occupation:
A 50%
B 50%
Order
Spatial
Temporal
Short Range
Ordered
Crystals*/
Quasicrystals
Glasses#
Long Range
Disordered
Ordered
Disordered
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
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 106 K/s for amorphization
Silicates amorphizes during air cooling
CRYSTALS
Non-molecular
Molecular
Molecule held together by primary
covalent bonds
Intermolecular bonding is Van der walls
COVALENT
IONIC
METALLIC
IONIC
METALLIC
kJ/mol
250
Electrostatic
Hydrogen bond
20
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
BCC
Li, Na, K , Ti, Zr, Hf, Nb, Ta, Cr, Mo, W, Fe (below 910C),
FCC
CLOSE PACKING
FCC
HCP
+
HCP
Atoms: (0,0,0), (, ,)
6
CV
a
4
h
6
CV
a
12
2
h CF VC
a
3
IDEAL c/a
c 2h
2
2
1.632
a a
3
a = 2r
BCC*
CCP
3a 4r
2a 4r
DC
HCP
3
a = 2r
a 2r
2
4
c 4r
3
Atoms / cell
12
12
3
8
3
16
2
6
= 0.52
= 0.68
Packing fraction
2
6
= 0.74
= 0.34
= 0.74
SC
(100) 1/a2
= 1/a2
FCC
BCC
2/a2
= 2/a2
1/a2
= 1/a2
2/a2
= 1.414/a2
2/a2
= 1.414/a2
4/(3a2) = 2.309/a2
1/(3a2) = 0.577/a2
Order (111) < (110) < (100) (110) < (100) < (111)
(100)
(110)
(111)
SC
a
FCC
2a
2a
2a
2a
BCC
a
2a
2a
FCC
BCC
Atoms /
Area
Area / Area
Atoms /
Area
Area / Area
Atoms /
Area
Area / Area
1/a2
/4 = 0.785
2/a2
/4 = 0.785
1/a2
3/16 =
0.589
(110) 2/(2a2)
0.707(/4) =
0.555
2/a2
2/8 = 0.555
2/a2
32/16 =
0.833
(111) 1/(3a2)
0.577(/4) =
0.453
4/(3a2)
(100)
3/16 =
0.34
VOIDS
FCC
TETRAHEDRAL
Vtetrahedron
1
Vcell
24
OCTAHEDRAL
At body centre
{, , }
+ face centering translations
Voctahedron
1
Vcell
6
FCC- OCTAHEDRAL
, 0} = {1, 1, } {0, 0, }
FCC voids
Position
Voids / cell
Voids / atom
Tetrahedral
Body centre: 1 (, , )
Octahedral
Size of the largest atom which can fit into the tetrahedral void of FCC
CV = r + x
6
erx
4
x
e 2r
r
Radius of the
new atom
3
1 ~ 0.225
2
Size of the largest atom which can fit into the Octahedral void of FCC
2r + 2x = a
2 1 ~ 0.414
2 a 4r
VOIDS
HCP
TETRAHEDRAL
OCTAHEDRAL
Octahedral voids
Tetrahedral void
Central atom
Check below
HCP voids
Position
Voids /
cell
Voids / atom
Tetrahedral
Octahedral
( ,), (,,)
VOIDS
BCC
Distorted TETRAHEDRAL
Distorted OCTAHEDRAL**
a3/2
a
a
a3/2
{0, 0, })
BCC voids
Distorted
Tetrahedral
Distorted
Octahedral
Position
Four on each face: [(4/2) 6 = 12] (0, , )
Face centre: (6/2 = 3) (, , 0)
Edge centre: (12/4 = 3) (, 0, 0)
Voids /
cell
Voids /
atom
12
a3/2
a2 a2
5
From the right angled triange OCM: OC
arx
16 4
4
For a BCC structure:
3a 4r ( a
5 4r
x
r x
4 3
r
4r
3
5
1 0.29
3
OB
a3/2
a
0.5a
2
OA
2a
.707a
2
This implies:
a
OB r x
2
4r
rx
2 3
BCC : 3a 4r
x 2 3
1 0.1547
r 3
FCC
Fe
FCC
Void (Oct)
1.292 A
FeFCC
Fe
xFCC
(oct ) 0.534 A
r 0.77 A
C
BCC
Fe
rBCC
1.258 A
FeBCC
x
x
Fe
BCC
Fe
BCC
(d .tet ) 0.364 A
(d .oct ) 0.195 A
Fe
xBCC
(d .tet )
0.29
Fe
rBCC
Fe
xBCC
(d .oct )
0.155
Fe
rBCC
Ignoring the atom sitting at B and assuming the interstitial atom touches the atom at A
2a
OA r x A
2
2 6r
r xA
3
Fe
BCC
1.258 A
BCC : 3a 4r
xA 2 6
1
0.6329
r 3
OX x A 0.796 A
OY xB 0.195 A
Fe
BCC
(d .tet ) 0.364 A
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
FCC
Element Added
Solid solution
Interstitial
Substitutional
Ordered
Chemical
compounds
Electron compounds
specific e/a ratio [21/14, 21/13, 21/12]
CuZn, Fe5Zn21, Au3Sn
Etc.
Zintl
Chemical
Phases:
compounds
Electrochemical compounds
Solid solution
Substitutional
Interstitial
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
Radius of
atoms ()
Valency
Electronegativity
Ag
FCC
1.44
1.9
Au
FCC
1.44
2.4
Cu
FCC
1.28
1.9
Ni
FCC
1.25
1.8
Ge
DC
1.22
1.8
Si
DC
1.18
1.8
System
Ag-Au
Cu-Ni
Ge-Si
A continuous series of solid solutions may not form even if the above
conditions are satisfied e.g. Cu- Fe
35% Zn in Cu
Zn
Cu
FCC
Valency 1
1% Cu
in Zn
HCP
Valency 2
High T disordered
BCC
G = H TS
470C
Sublattice-1
Sublattice-2
Low T ordered
SC
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, Cu3Au..]
Ordered solid solutions are in-between solid solutions and chemical
compounds
Degree of order decreases on heating and vanishes on reaching
disordering temperature [ compound]
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 )