STRUCTURE OF SOLIDS

❑ Types of solids based on structure

❑ Types of solids based on bonding
 UNIVERSE STRONG
WEAK
HYPERBOLIC ELECTROMAGNETIC
EUCLIDEAN SPACE ENERGY GRAVITY
SPHERICAL
nD + t
PARTICLES FIELDS

METAL
ATOMIC NON-ATOMIC
SEMI-METAL BAND STRUCTURE
SEMI-CONDUCTOR
INSULATOR STATE / VISCOSITY

LIQUID
GAS SOLID LIQUID CRYSTALS
STRUCTURE

AMORPHOUS QUASICRYSTALS RATIONAL CRYSTALS

APPROXIMANTS
SIZE

NANO-QUASICRYSTALS NANOCRYSTALS
 CLASSIFICATION OF SOLIDS BASED ON ATOMIC
ARRANGEMENT

AMORPHOUS QUASICRYSTALS CRYSTALS

Ordered Ordered Ordered

+ + +
Periodic Periodic 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

 THE ENTITY IN QUESTION

GEOMETRICAL PHYSICAL
E.g. Atoms, Cluster of Atoms E.g. Electronic Spin, Nuclear spin
Ions, etc.

ORDER

ORIENTATIONAL POSITIONAL

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

ORDER

TRUE PROBABILISTIC
ORIENTATIONAL
Perfect

Average

Perfect

POSITIONAL

Average

Positionally ordered A B

PROBABILISTIC
Probability of
OCCUPATION occupation:
A → 50%
Probabilistically ordered B → 50%
 Order

Spatial Temporal
 Range of Spatial Order

Short Range (SRO) Long Range Order (LRO)

Class/ Short Range Long Range

example(s)  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
 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

Molecular Non-molecular

▪ Molecule held together by primary COVALENT

covalent bonds
▪ Intermolecular bonding is Van der walls IONIC

METALLIC

CLASSIFICATION OF SOLIDS BASED ON BONDING

COVALENT IONIC METALLIC

Approximate Strengths of Interactions
between atoms

Bond Type kJ/mol

Covalent Bond 250

Electrostatic 5

van der Waals 5

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 - 1410ºC), Cu, Ag, Au, Ni, Pd, Pt

❑ BCC → Li, Na, K , Ti, Zr, Hf, Nb, Ta, Cr, Mo, W, Fe (below 910ºC),
❑ HCP → Be, Mg, Ti, Zr, Hf, Zn, Cd
❑ Others → La, Sm Po, α-Mn, Pu
 CLOSE PACKING FCC

+ + =

A B C FCC
Note: Atoms are coloured differently but are the same
 Shown displaced for clarity
HCP

+ + =

A B A
HCP

Unit cell of HCP (Rhombic prism)

Note: Atoms are coloured differently but are the same

 Atoms: (0,0,0), (⅔, ⅓,½)

Note: diagrams not to scale

 6
CV = a
4
h 6
CV = a
12
2
h = CF + VC = a
3

c 2h 2
IDEAL c/a = =2 = 1.632
a a 3
 PACKING FRACTION / Efficiency

Volume occupied by atoms

Packing Fraction =
Volume of Cell

SC* BCC* CCP DC HCP

3
Relation between atomic radius (r) a = 2r 3a = 4r 2a = 4r a = 2r a = 2r
and lattice parameter (a) 4 2
c = 4r
3

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  3 2 3 2
6 8 6 16 6
= 0.52 = 0.68 = 0.74 = 0.34 = 0.74

* Crystal formed by monoatomic decoration of the lattice

ATOMIC DENSITY (atoms/unit area)

SC FCC BCC
(100) 1/a2 = 1/a2 2/a2 = 2/a2 1/a2 = 1/a2
(110) 1/(a22) = 0.707/a2 2/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
2a 2a

FCC a a

2a 2a

BCC

a
2a 2a
ATOMIC DENSITY (area covered by atoms/unit area)

SC FCC BCC
Atoms / Area / Area Atoms / Area / Area Atoms / Area / Area
Area Area Area
(100) 1/a2 /4 = 0.785 2/a2 /4 = 0.785 1/a2 3/16 =
0.589
(110) 2/(2a2) 0.707(/4) = 2/a2 2/8 = 0.555 2/a2 32/16 =
0.555 0.833
(111) 1/(3a2) 0.577(/4) = 4/(3a2) /(23) =0.9068 1/(3a2) 3/16 =
0.453 0.34
 FCC VOIDS

TETRAHEDRAL OCTAHEDRAL

¼ way along body diagonal At body centre

{¼, ¼, ¼}, {¾, ¾, ¾} {½, ½, ½}
+ face centering translations + face centering translations
1
Vtetrahedron = Vcell 1
Voctahedron = Vcell
24 6
Note: Atoms are coloured differently but are the same
 FCC- OCTAHEDRAL

Site for octahedral void

{½, ½, ½} + {½, ½, 0} = {1, 1, ½}  {0, 0, ½}

Equivalent site for an
Face centering translation
octahedral void

Note: Atoms are coloured differently but are the same

FCC voids Position Voids / cell Voids / atom

¼ way from each vertex of the cube

Tetrahedral along body diagonal <111> 8 2
→ ((¼, ¼, ¼))
• Body centre: 1 → (½, ½, ½)
Octahedral 4 1
• Edge centre: (12/4 = 3) → (½, 0, 0)
Size of the largest atom which can fit into the tetrahedral void of FCC

CV = r + x Radius of the
new atom
e 6
e=r+x
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 2a = 4r

x
r
= ( )
2 − 1 ~ 0.414
 HCP VOIDS

TETRAHEDRAL OCTAHEDRAL

Coordinate s : (0,0, 3 8 ), (0,0, 5 8 ), ( 2 3 , 13 , 18 ), ( 2 3 , 13 , 7 8 ) Coordinates: (⅓ ⅔,¼), (⅓,⅔,¾)

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 vice-
versa) 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), (⅔, ⅓,½)

Check below

Voids /
HCP voids Position Voids / atom
cell
(0,0,3/8), (0,0,5/8), (⅔, ⅓,1/8),
Tetrahedral 4 2
(⅔,⅓,7/8)
Octahedral • (⅓ ⅔,¼), (⅓,⅔,¾) 2 1
A

A
 BCC VOIDS

Distorted TETRAHEDRAL Distorted OCTAHEDRAL**

a3/2

a
a a3/2

Coordinates of the void:

{½, 0, ¼} (four on each face) Coordinates of the void:
{½, ½, 0} (+ BCC translations: {0, 0, ½})
Illustration on one face only

rvoid / ratom = 0.29 rVoid / ratom = 0.155

Note: Atoms are coloured differently but are the same ** Actually an atom of correct size touches only
the top and bottom atoms
 {0, 0, ½})

Voids / Voids /
BCC voids Position
cell atom

Distorted
• Four on each face: [(4/2)  6 = 12] → (0, ½, ¼) 12 6
Tetrahedral

Distorted • Face centre: (6/2 = 3) → (½, ½, 0)

6 3
Octahedral • Edge centre: (12/4 = 3) → (½, 0, 0)
 a BCC: Distorted Tetrahedral Void

a3/2

a2 a2 5
From the right angled triange OCM: OC = + = a=r+x
16 4 4
4r
For a BCC structure: 3a = 4r ( a = )
3

5 4r x  5 
= r + x  =  − 1 = 0.29
4 3 r  3 
Distorted Octahedral Void
a 2a
OB = = 0.5a OA = = .707 a
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
a3/2

This implies:
a
a
OB = r + x =
2
4r
r+x= BCC : 3a = 4r
2 3

x 2 3 
=  − 1 = 0.1547
r  3 
FCC
 Void (Oct)
r Fe
FCC = 1.292 A
FeFCC C

Fe
xFCC (oct ) = 0.534 A N

 O
r = 0.77 A
C

Relative sizes of voids w.r.t to atoms

BCC
  Fe

(d .tet ) = 0.364 A
Fe xBCC (d .tet )
= 0.29
Fe
rBCC = 1.258 A x BCC
Fe
rBCC

 Fe
xBCC (d .oct )
FeBCC x Fe
BCC (d .oct ) = 0.195 A Fe
rBCC
= 0.155
Ignoring the atom sitting at B and assuming the interstitial atom touches the atom at A

2a
OA = r + x A = r Fe
BCC = 1.258 A
2
2 6r BCC : 3a = 4r
r + xA =
3
xA  2 6 
= − 1 = 0.6329
r  3 

OX = xA = 0.796 A OY = xB = 0.195A x Fe
BCC (d .tet ) = 0.364 A
Summary of void sizes

rvoid / ratom
SC BCC FCC DC
Octahedral 0.155
0.414 -
(CN = 6) (distorted)
Tetrahedral 0.29 1
0.225
(CN = 4) (distorted) (½,½,½) & (¼, ¼, ¼)
Cubic
0.732
(CN = 8)
 FCC

• The primitive UC for the FCC lattice is a Rhombohedron

• Primitive unit cell made of 2T + 1O
• Occupies ¼ the volume of the cell

Note: Atoms are coloured differently but are the same

 ADDITION OF ALLOYING ELEMENTS

Segregation / phase separation

1
Interstitial
Element Added 2 Solid solution
Substitutional Ordered
3
Compound /Intermediate structure
(new crystal structure)
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

3 Determined by Rx / RM ratio
Chemical W2C, VC, Fe4N etc.
compounds
Electron compounds
specific e/a ratio [21/14, 21/13, 21/12]
CuZn, Fe5Zn21, Au3Sn

Size Factor compounds

Laves phases, Frank-Kasper Phases
Etc.
 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
 2 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 Radius of
System Valency Electronegativity
structure atoms (Å)
Ag FCC 1.44 1 1.9
Ag-Au
Au FCC 1.44 1 2.4

Cu FCC 1.28 1 1.9

Cu-Ni
Ni FCC 1.25 2 1.8

Ge DC 1.22 4 1.8
Ge-Si
Si DC 1.18 4 1.8

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

Cu Zn
1% Cu
FCC in Zn HCP
Valency 1 Valency 2
 In a strict sense this is not a crystal !!
Ordered Solid solution

High T disordered

BCC

470ºC
G = H − TS

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 Å), N (r = 0.71 Å), H (r = 0.46 Å)