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STRUCTURE OF SOLIDS

Types of solids based on structure

Types of solids based on bonding

UNIVERSE

STRONG
WEAK
ELECTROMAGNETIC

HYPERBOLIC
EUCLIDEAN
SPHERICAL

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

CLASSIFICATION OF SOLIDS BASED ON ATOMIC


ARRANGEMENT
AMORPHOUS
Ordered
+
Periodic

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!!

CLASSIFICATION OF SOLIDS BASED ON ATOMIC


ARRANGEMENT
AMORPHOUS

QUASICRYSTALS

CRYSTALS

ADDITIONAL POSSIBLE STRUCTURES

Incommensurately
Modulated structures

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
POSITIONAL

ORIENTATIONAL

Order-disorder of: POSITION, ORIENTATION, ELECTRONIC & NUCLEAR SPIN

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

Range of Spatial Order


Short Range (SRO)
Class/
example(s)
Crystals*/
Quasicrystals
Glasses#
Crystallized
virus$
Gases

Long Range Order (LRO)

Short Range
Ordered
Disordered

Long Range
Ordered
Disordered

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

Factors affecting the formation of the amorphous state


When primary bonds are 1D or 2D and secondary bonds aid in the
formation of the crystal
The crystal structure is very complex

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

CLASSIFICATION OF SOLIDS BASED ON BONDING

COVALENT

IONIC

METALLIC

Approximate Strengths of Interactions


between atoms
Bond Type
Covalent Bond

kJ/mol
250

Electrostatic

van der Waals

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

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

FCC

CLOSE PACKING

Note: Atoms are coloured differently but are the same

FCC

Shown displaced for clarity

HCP
+

Unit cell of HCP (Rhombic prism)


Note: Atoms are coloured differently but are the same

HCP

Atoms: (0,0,0), (, ,)

Note: diagrams not to scale

6
CV
a
4
h

6
CV
a
12
h CF VC

IDEAL c/a

2
a
3

c 2h
2

2
1.632
a a
3

PACKING FRACTION / Efficiency

Volume occupied by atoms


Packing Fraction
Volume of Cell
SC*
Relation between atomic radius (r)
and lattice parameter (a)

a = 2r

BCC*

CCP

3a 4r

2 a 4r

DC

HCP

3
a 2r
4

a = 2r
c 4r

Atoms / cell

Lattice points / cell

No. of nearest neighbours

12

12

3
8

3
16

2
6

= 0.52

= 0.68

Packing fraction

* Crystal formed by monoatomic decoration of the lattice

2
6

= 0.74

= 0.34

2
3

= 0.74

ATOMIC DENSITY (atoms/unit area)

SC
(100) 1/a2

= 1/a2

FCC
2/a2

(110) 1/(a22) = 0.707/a2 2/a2

BCC

= 2/a2

1/a2

= 1/a2

= 1.414/a2

2/a2

= 1.414/a2

(111) 1/(3a2) = 0.577/a2 4/(3a2) = 2.309/a2

1/(3a2) = 0.577/a2

Order (111) < (110) < (100) (110) < (100) < (111)

(111) < (100) < (110)

(100)

(110)

(111)

SC
a

FCC

2a

2a

2a

2a

BCC
a

2a

2a

ATOMIC DENSITY (area covered by atoms/unit area)

SC

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)

/(23) =0.9068 1/(3a2)

3/16 =
0.34

VOIDS

FCC
TETRAHEDRAL

way along body diagonal


{, , }, {, , }
+ face centering translations

Vtetrahedron

1
Vcell
24

Note: Atoms are coloured differently but are the same

OCTAHEDRAL

At body centre
{, , }
+ face centering translations

1
Voctahedron Vcell
6

FCC- OCTAHEDRAL

Site for octahedral void


{, , } + {,

, 0} = {1, 1, } {0, 0, }

Face centering translation

Note: Atoms are coloured differently but are the same

Equivalent site for an


octahedral void

FCC voids

Position

Voids / cell

Voids / atom

Tetrahedral

way from each vertex of the cube


along body diagonal <111>
((, , ))

Octahedral

Body centre: 1 (, , )
Edge centre: (12/4 = 3) (, 0, 0)

Size of the largest atom which can fit into the tetrahedral void of FCC
CV = r + x

Radius of the
new atom

6
erx
4
x 3
e 2r
1 ~ 0.225
r 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

Coordinates : (0,0, 3 8 ), (0,0, 5 8 ), ( 2 3 , 13 , 18 ), ( 2 3 , 13 , 7 8 )

OCTAHEDRAL

Coordinates: ( ,), (,,)

These voids are identical to the ones found in FCC


Note: Atoms are coloured differently but are the same

The other orientation of the tetrahedral void

Octahedral voids occur in 1 orientation, tetrahedral voids occur in 2 orientations


Note: Atoms are coloured differently but are the same

Note: Atoms are coloured differently but are the same

Octahedral voids

Tetrahedral void

Note: Atoms are coloured differently but are the same

Voids/atom: FCC HCP


as we can go from FCC to HCP (and viceversa) by a twist of 60 around a central atom of
two void layers (with axis to figure)

Central atom

Atoms in HCP crystal: (0,0,0), (, ,)

Check below
HCP voids

Position

Voids /
cell

Voids / atom

Tetrahedral

(0,0,3/8), (0,0,5/8), (, ,1/8),


(,,7/8)

Octahedral

( ,), (,,)

VOIDS

BCC
Distorted TETRAHEDRAL

Distorted OCTAHEDRAL**

a3/2

a
a

a3/2

Coordinates of the void:


{, 0, } (four on each face)

Coordinates of the void:


{, , 0} (+ BCC translations: {0, 0, })
Illustration on one face only

rvoid / ratom = 0.29


Note: Atoms are coloured differently but are the same

rVoid / ratom = 0.155


** Actually an atom of correct size touches only
the top and bottom atoms

{0, 0, })

BCC voids

Position

Voids /
cell

Voids /
atom

Distorted
Tetrahedral

Four on each face: [(4/2) 6 = 12] (0, , )

12

Distorted
Octahedral

Face centre: (6/2 = 3) (, , 0)


Edge centre: (12/4 = 3) (, 0, 0)

BCC: Distorted Tetrahedral Void

a3/2

a2 a2
5
From the right angled triange OCM: OC

arx
16 4
4
For a BCC structure:

3a 4r ( a

4r
3

5 4r
x 5
r x
1 0.29
4 3
r 3

Distorted Octahedral Void

OB

a
0.5a
2

OA

2a
.707 a
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

a3/2

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

Relative sizes of voids w.r.t to atoms

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 xA 0.796 A

OY xB 0.195A

Fe
BCC

(d .tet ) 0.364 A

Summary of void sizes


rvoid / ratom

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

FCC

The primitive UC for the FCC lattice is a Rhombohedron


Primitive unit cell made of 2T + 1O
Occupies the volume of the cell
Note: Atoms are coloured differently but are the same

ADDITION OF ALLOYING ELEMENTS

Segregation / phase separation


1

Interstitial
2

Element Added

Solid solution
Substitutional

Compound /Intermediate structure


(new crystal structure)

Ordered

1 Segregation / phase separation

The added element does not dissolve in the parent/matrix phase


in a polycrystal may go to the grain boundary

Valency compounds (usual)


Electrochemical compounds : Zintl

Mg2Sn, Mg2Pb, MgS etc.


Interstitial Phases: Hagg
Determined by Rx / RM ratio
W2C, VC, Fe4N etc.

Chemical
compounds

Electron compounds
specific e/a ratio [21/14, 21/13, 21/12]
CuZn, Fe5Zn21, Au3Sn

Etc.

Size Factor compounds


Laves phases, Frank-Kasper Phases

Zintl
Chemical
Phases:
compounds
Electrochemical compounds

Different crystal lattice as compared to the components


Each component has a specific location in the lattice
AnBm
Different properties than components
Constant melting point and dissociation temperature
Accompanied by substantial thermal effect

Solid solution

Substitutional

Interstitial

The mixing is at the atomic scale and is analogous to a liquid solution


NOTE
Pure components A, B, C
Solid solutions , ,
Ordered Solid solutions , ,

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

Examples of pairs of elements satisfying Hume Rothery rules and forming


complete solid solution in all proportions
Crystal
structure

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

Counter example of a pair of elements not forming solid solution in all


proportions

35% Zn in Cu

Zn

Cu
FCC
Valency 1

1% Cu
in Zn

HCP
Valency 2

In a strict sense this is not a crystal !!

Ordered Solid solution


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]

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 )