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APL 102
Introduction to Materials Science & Engineering

Alloying: Substitutional solid solution & Ionic solids

Concepts: Hume-Rothery rules; SS strengthening, ligancy, radius ratio

Lecture 10
 Recap
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Alloying (Solid Solutions) - A crystalline phase consisting of two or more elements

Solid solubility limited by: Size difference & vacant positions
Interstitial Solutions - Ceramic crystals
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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
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Solubility in ‘solid solution (alloying)’
 Hume-Rothery Rules for Extensive Solid Solution
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(Unlimited solubility)
Interstitial solid solution Substitutional solid solution
1. Structure factor
Crystal structure of the two elements should be the same

2. Size factor:
Size of the two elements should not differ by more than 15%

3. Electronegativity factor:
Electronegativity difference between the elements should be small

4. Valency factor:
Valency of the two elements should be the same
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Additional rule:

Element with higher valency is dissolved more in an element

of lower valency rather than vice versa.
 Hume-Rothery Parameters
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System Crystal Radius of Valency Electro-

structure atoms, Ǻ negativity

Ag-Au Ag FCC 1.44 1 1.9

Au FCC 1.44 1 1.9

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

Zn HCP 1.31 2 1.5

All three systems exhibit complete solid solubility

Only 5-7% of Cu is soluble in Ag at 725 °C

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BRASS (70-30)
Cu + Zn
FCC HCP
Unfavourable structure factor??
Jewellery, taps, door handles,
marine hardware's etc.

Limited Solubility:

Max solubility of Cu in Zn: 1 wt% Cu

Max Solubility of Zn in Cu: 35 wt% Zn

IIT Delhi 1% of Cu in Zn

35% Zn in Cu

Cu, FCC Valency: 1 Zn, HCP Valency: 2

Additional rule:

Element with higher valency is dissolved more in an element of lower

valency rather than vice versa.

Hume Rothery rules are guiding principles

This cannot be rigorous as exceptions are there
 Ordered and Random Substitutional solid solution
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Random/disordered Ordered Solid Solution

Solid Solution

Location of solute and solvent atoms

 Ordered/disordered transformation
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Typically high temperature phase is disordered while low

temperature is ordered phase

Let us see an example..

 Ordered and random substitutional solid solution
β-Brass: (50 at% Zn, 50 at% Cu)
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Disordered solid solution of β-Brass:

Above
Corner and center both have 50%
470˚C
probability of being occupied by Cu or Zn

470˚C

Ordered solid solution of β-Brass:

Below
470˚C
Corners are always occupied by Cu,
centers always by Zn
Note: ordered and disordered phase have different crystal structures
The structure of ordered alloy is different from that of both components
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Question for thought?

What mixing of elements or alloying can lead to?

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Solid solution hardening
 Foreign atom distort the host lattice and generate the stress

Substitutional element of
Smaller and Larger size than
the host atom size
Compressive stress Tensile stress

 Interstitial or substitutional impurities cause lattice strain and interact with

dislocation strain fields thereby hinder dislocation motion

 Impurities diffuse and segregate around dislocation to find atomic sites more
suited to their radii: Reduces strain energy + anchors dislocation
 Example: Solid solution strengthening
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Brass: Strength increases with wt% Zn

Empirical relation:  y ~ C 1 / 2
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Question for thought?

What happens when ions of dissimilar size are mixed together?

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Ionically bonded solids

(non-directional, bonds b/w ions of different sizes,
ionic crystals: packing of different size spheres)

Ionic bonds are formed due to unequal sharing of electrons

IIT Delhi Ionic solids
Cation radius: R+
Anion radius: R-
Usually R   R 

1. Cation and anion attract each other

2. Cation and anion spheres touch each other

3. Ionic bonds are non-directional

1, 2, 3 => Close packing of unequal spheres

Ionic crystals are not truly close packed in the sense what we had seen for FCC/HCP
 Definition
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Coordination number or Ligancy:

The number of anions touching the cations is known as Ligancy

 Ionic Solids
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Local coordination-------- Long range arrangement------- Ionic crystal

(how many anions surround a cation)

Rules for Local packing geometry (stable configuration)

1. Anions and cations considered as hard spheres always touch each other
2. Anions generally will not touch, but may be close enough to be in contact
with each other in a limiting situation
3. A central cation is surrounded by as many anions as possible for the
maximum reduction in electrostatic energy
 Rules for local stable configuration
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No rattling: Cations should not be smaller than the void formed by anions

Cation size larger than void: this is required so that anions do not touch each other

Choose the largest possible coordination

 Ligancy as a Function of Radius Ratio
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Ligancy Range of radius ratio Configuration

2 0.0 ― 0.155 Linear

Lower limit decided by current coordination Upper limit decided by next possible higher coordination
3 0.155 ― 0.225 Triangular

4 0.225 ― 0.414 Tetrahedral

6 0.414 ― 0.732 Octahedral

8 0.732 ― 1.0 Cubic

12 1.0 FCC or HCP

 Effect of radius ratio
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Rc Rc Rc
 0.155  0.155  0.155
Ra Ra Ra

Unstable Critically stable/limiting Stable

Anions not touching the Anions touching

Anions touching central cation
central cation, the central cation
Anions not touching each other
Anions touching each other Anions touching

Rc Rc
 0.155  Ligancy  2  0.155  Ligancy  3
Ra Ra
 Long range arrangements
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1. Overall electrical neutrality: net charge should be zero (any charge

from local configuration can be offset by long range order)

2. Ions are packed as closely as possible consistent with the local

coordination

3. Avoid cation-cation repulsion if possible