IIT Delhi

APL 102
Introduction to Materials Science & Engineering

Voids in Non-close Packed Structures & Alloying

Concepts: size of tetra- & octa- hedral voids, distorted voids, solid solution

Lecture 9
 Recap
IIT Delhi HCP crystal structure Planar Density – (atoms/unit area)

Voids in crystals CCP (FCC)

Motif

Packing Fraction

Volume occupied by atoms
Volume of Cell
 Size of the largest atom which can fit into the
tetrahedral void of FCC
IIT Delhi

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
IIT Delhi

2r + 2x = a

2a  4r

x
r
  
2  1 ~ 0.414
IIT Delhi Some facts
Thus, size of octahedral void is bigger than the size of
tetrahedral void

A foreign atom of bigger size would be more comfortable

in octahedral position than tetrahedral position

This will have an strong implication on solubility and hence

on properties
IIT Delhi
Question for thought?

Are the voids same in the other closely packed structure?

Not really!!
The stacking sequence is different and hence the void volume and location
is different
IIT Delhi

Voids in HCP
 Tetrahedral voids in HCP
IIT Delhi

The other orientation of the tetrahedral void

Position of voids: (0,0,3/8), (0,0,5/8), (⅔, ⅓,1/8), (⅔,⅓,7/8)

These voids are identical to the ones found in FCC

IIT Delhi

Tetrahedral voids occur in 2 orientations

Octahedral voids occur in 1 orientation

IIT Delhi
Octahedral voids in HCP
IIT Delhi

How many octahedral and tetrahedral voids

per unit cell in HCP crystal?
 Summary of voids in HCP
IIT Delhi

Voids / Voids /
HCP voids Position
cell atom
(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
 Illustration of Space filling
IIT Delhi

Octahedral voids

Tetrahedral void
IIT Delhi

Voids in non-close packed structure

IIT Delhi
Voids in BCC

Distorted tetrahedral voids

Distorted octahedral voids

C atom in BCC iron prefers to sit in non-regular octahedral void

even though it is of smaller size as compared to tetrahedral Void
 Tetrahedral voids in BCC
IIT Delhi

a a3/2

Coordinates of the void:

(½, 0, ¼) (four on each face)
 Octahedral voids in BCC
IIT Delhi

a3/2

Coordinates of the void:

(½,½, 0)
 Octahedral voids in BCC
IIT Delhi

{0, 0, ½})

Coordinates of the void:

{0, 0, ½}
IIT Delhi

How many octahedral and tetrahedral voids per unit cell in BCC crystal?
 Summary of position of voids in BCC
IIT Delhi

Illustration on single face

TV OV
 Summary of voids in BCC
IIT Delhi

Voids / Voids /
BCC voids Position
cell atom

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

Non-regular • Face centre: (6/2 = 3)  (½, ½, 0)

6 3
Octahedral • Edge centre: (12/4 = 3)  (½, 0, 0)
 Size of the largest atom which can fit into the
tetrahedral void of BCC
IIT Delhi

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 
 Size of the largest atom which can fit into the
Octahedral void of FCC
IIT Delhi

a 2a
OB   0.5a OA   .707a
2 2

a3/2 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

Octahedral void in BCC is also known as linear void

 Size of the largest atom which can fit into the
Octahedral void of FCC
IIT Delhi

From the pervious slide

a
a3/2 OB  r  x 
2
4r
rx BCC : 3a  4r
a 2 3

x 2 3 
   1  0.1547
r  3 
 Summary
IIT Delhi

 Octahedral and tetrahedral voids in BCC are distorted in nature.

 There are 6 tetrahedral and 3 octahedral voids per atom in BCC structure.
These numbers are more than what we had found in CCP crystals.

 Octahedral void in BCC is also known as linear void.

 Unlike CCP, the size of tetrahedral void in BCC is greater than the size of
octahedral void

BCC FCC
Octahedral 0.155 (distorted) 0.414
Tetrahedral 0.29 (distorted) 0.225
IIT Delhi
Some facts
CCP and HCP crystals are close packed crystals (packing fraction of 0.74):
They have close packed planes and directions

The voids observed in CCP and HCP crystals are regular tetrahedron and
regular Octahedron

Coordination number for above two: 12

BCC crystal is not a close packed structure. It has (110) close packed plane,
but have <111> direction as a close packed direction

The voids in BCC are non-regular tetrahedron and non regular Octahedron
IIT Delhi
Question for thought?

Why voids are important in crystals structures?

Second/Third type of atom sits into that void

Alloying (Solid Solution) & Ceramics

IIT Delhi
Contents

 Packing of atoms in crystals: FCC, HCP and

BCC crystals, stacking sequence

 Close packed planes and directions, Packing fraction

 Voids in solids: understand structure and position of

voids in above crystal structures

 Implications of voids
 Alloying (Solid Solutions)
IIT Delhi

 Most materials consist of some second element

• Usually to obtain improvement in properties

 Alloys are stronger than pure metals

 Mixing takes place at atomic/molecular level

Example
• Steel: Fe-C alloy (< 2 wt% C)
• Brass: Cu-Zn alloy (up to ~50 wt% Zn)
• Bronze: Cu-Sn alloy (up to ~12 wt% Sn)
IIT Delhi
Solubility in ‘solid solution (alloying)’ of elements
 Solid Solution
IIT Delhi

A single crystalline phase consisting of two or more elements is called a solid solution

Substitutional Solid solution Interstitial solid solution

of Cu and Zn (FCC): Solute of C in Fe (BCC): Solute
occupies host atom site occupies interstices
IIT Delhi
Substitutional solid solution

Unlike interstitial solid solution, in substitutional solid solution solubility

can range from 0 to 100 %

There are set of empirical rules that governs this: Hume Rothery Rules
 Interstitial solid solution
IIT Delhi

Factors limiting solid solubility

Size difference between solute and solvent

Available vacant positions

 Ceramic crystals
IIT Delhi

The hardest, most refractory materials of engineering

Structure of ceramics often have atoms arranged in a BCC, FCC, or HCP structure with a
second and/or third type of atom inserted into the Interstitial sites of the first

Materials: engineering, science, processing and design, 2nd edition Copyright (c)2010 Michael Ashby, Hugh Shercliff, David Cebon
 Diamond Cubic (DC) Structure
IIT Delhi

Unit Cell of Diamond

Essentially an FCC lattice with an

additional atom in each of its
tetrahedral interstices

Materials: engineering, science, processing and design, 2nd edition Copyright (c)2010 Michael Ashby, Hugh Shercliff, David Cebon
 Silicon Carbide (SiC) Structure
IIT Delhi

Structure of silicon carbide; same DC

structure as diamond with
different chemical composition

Materials: engineering, science, processing and design, 2nd edition Copyright (c)2010 Michael Ashby, Hugh Shercliff, David Cebon
 Oxides with Rocksalt (Halite) Structure
IIT Delhi

Have the formula MO, where M

is a metal ion

The oxygen packs in an FCC

structure and metal atoms
occupy the octahedral holes

Materials: engineering, science, processing and design, 2nd edition Copyright (c)2010 Michael Ashby, Hugh Shercliff, David Cebon
 Oxides with a Corundum Structure
IIT Delhi

M2O3 formula with M

being metal ions

Oxygen atoms close-packed in an HCP

structure with metal atoms
occupying 2/3 of octahedral holes

Materials: engineering, science, processing and design, 2nd edition Copyright (c)2010 Michael Ashby, Hugh Shercliff, David Cebon
 Oxides with Fluorite Structure
IIT Delhi

Formula of MO2, but unlike in earlier

oxides, the metal atoms (M) are
bigger than the oxygen atoms

The metal atoms form a close-packed

FCC structure and the oxygen atoms
fill the tetrahedral interstices

Materials: engineering, science, processing and design, 2nd edition Copyright (c)2010 Michael Ashby, Hugh Shercliff, David Cebon
 Question for thought?
IIT Delhi

Why alloys should be made at all?