The Science and Engineering

of Materials, 4th ed
Donald R. Askeland – Pradeep P. Phulé

Chapter 8 – Solid Solutions and Phase Equilibrium

 Objectives of Chapter 8
 The goal of this chapter is to describe the underlying
physical concepts related to the structure of matter.

 To examine the relationships between structure of

atoms-bonds-properties of engineering materials.

 Learn about different levels of structure i.e. atomic

structure, nanostructure, microstructure, and
macrostructure.

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 Chapter 8 Outline
 8.1 Solubility and Solid Solutions
 8.2 Phases and the Phase Diagram
 8.3 Conditions for Unlimited Solid Solubility
 8.4 Solid-Solution Strengthening
 8.5 Isomorphous Phase Diagrams
 8.6 Relationship Between Properties and the Phase Diagram
 8.7 Solidification of a Solid-Solution Alloy
 8.8 Fe-Fe3C phase diagram
 8.9 Classification of Steels
 8.10 Classification of Cast Irons
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 Section 8.1 Solubility and Solid Solutions

 Solubility - The amount of one material that will completely dissolve in a

second material without creating a second phase.

 Unlimited solubility - When the amount of one material that will dissolve in
a second material without creating a second phase is unlimited.

 Limited solubility - When only a maximum amount of a solute material can

be dissolved in a solvent material.

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 Section 8.2 Phases and the Phase Diagram

 Phase - Any portion including the whole of a system, which is physically

homogeneous within it and bounded by a surface so that it is mechanically
separable from any other portions.

Illustration of phases and solubility: (a) The three forms of water – gas, liquid, and solid –
are each a phase. (b) Water and alcohol have unlimited solubility. (c) Salt and water have
limited solubility. (d) Oil and water have virtually no solubility.

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(a) Liquid copper and liquid nickel are completely soluble in each other. (b) Solid copper-
nickel alloys display complete solid solubility, with copper and nickel atoms occupying
random lattice sites. (c) In copper-zinc alloys containing more than 30% Zn, a second
phase forms because of the limited solubility of zinc in copper.
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 The solubility of zinc in
copper. The solid line
represents the solubility
limit; when excess zinc
is added, the solubility
limit is exceeded and
two phases coexist.

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 Gibbs phase rule - Describes the number of degrees of freedom, or the
number of variables that must be fixed to specify the temperature and
composition of a phase (2 + C = F + P, where pressure and temperature can
change, 1 + C = F + P, where pressure or temperature is constant). (C:
component, F: freedom, P: phase)

 Pressure-Temperature diagram (P-T diagram or unary phase diagram) - A

diagram describing thermodynamic stability of phases under different
temperature and pressure conditions (liquid, solid, and vapor phases).

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 Schematic unary phase
diagram for magnesium,
showing the melting and
boiling temperatures at
one atmosphere pressure.

2+C=F+P
C=1 → 3 = F + P
At A: P = 1 → F = 2
At B: P = 2 → F = 1
At X: P = 3 → F = 0

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 Section 8.3 Conditions for Unlimited Solid
Solubility

 Hume-Rothery rules - The conditions that an alloy or ceramic system must

meet if the system is to display unlimited solid solubility. Hume-Rothery’s
rules are necessary but are not sufficient for materials to show unlimited
solid solubility.

 Hume-Rothery rules:
- Size factor
- Crystal structure
- Valence
- Electronegativity

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MgO and NiO have similar crystal structures, ionic radii, and valences; thus the
two ceramic materials can form solid solutions.

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 Section 8.4 Solid-Solution Strengthening

 Solid-solution strengthening - Increasing the strength of a metallic material

via the formation of a solid solution.

 Dispersion strengthening - Strengthening, typically used in metallic

materials, by the formation of ultra-fine dispersions of a second phase.

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 The effects of several alloying
elements on the yield strength of
copper.
Nickel and zinc atoms are about the
same size as copper atoms, but
beryllium and tin atoms are much
different from copper atoms.
Increasing both atomic size
difference and amount of alloying
element increases solid-solution
strengthening.

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The effect of additions of zinc to copper on the properties of the solid-solution-
strengthened alloy. The increase in % elongation with increasing zinc content is not
typical of solid-solution strengthening.

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 Section 8.5 Isomorphous Phase Diagrams
 Binary phase diagram - A phase diagram for a system with two components.

 Ternary phase diagram - A phase diagram for a system with three

components.

 Isomorphous phase diagram - A phase diagram in which components

display unlimited solid solubility.

 Liquidus temperature - The temperature at which the first solid begins to

form during solidification.

 Solidus temperature - The temperature below which all liquid has

completely solidified.

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The equilibrium phase diagrams for the Cu-Ni and NiO-MgO systems.
The liquidus and solidus temperatures are shown for a Cu-40% Ni alloy.

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Systems with solid solution maxima and minima.

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 Example 8.1
Gibbs Rule for Isomorphous Phase Diagram
Determine the degrees of freedom in a Cu-40% Ni alloy at (a) 1300oC, (b)
1250oC, and (c) 1200oC.
Example 8.1 SOLUTION
This is a binary system (C = 2). Two components are Cu and Ni. Assuming a constant
pressure, (1 + C = F + P) can be used as follows:
(a) At 1300oC, P = 1, since only one phase (liquid) is present. . Thus:
1 + C = F + P So, 1 + 2 = F + 1 or F = 2
(b) At 1250oC, P = 2, since both liquid and solid are present. Now:
1 + C = F + P So, 1 + 2 = F + 2 or F = 1
(c) At 1200oC, P = 1, since only one phase, solid, is present. Again,
1 + C = F + P So, 1 + 2 = F + 1 or F = 2

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 A hypothetical binary phase
diagram between elements A
and B.
When an alloy is present in a
two-phase region, a tie line at
the temperature of interest
fixes the composition of the
two phases.
This is a consequence of the
Gibbs phase rule, which
provides only one degree of
freedom.

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 Example 8.2
Compositions of Phases in Cu-Ni Phase Diagram
Determine the composition of each phase in a Cu-40% Ni alloy at 1300oC, 1270oC,
1250oC, and 1200oC.
Example 8.2 SOLUTION
The vertical line at 40% Ni represents the overall
composition of the alloy:
- 1300oC: Only liquid is present. The liquid must
contain 40% Ni, the overall composition of the alloy.
- 1270oC: Two phases are present. The liquid
contains 37% Ni and the solid contains 50% Ni.
- 1250oC: Again two phases are present. The tie line
drawn at this temperature shows that the liquid
contains 32% Ni and the solid contains 45% Ni.
- 1200oC: Only solid α is present, so the solid must
contain 40% Ni.
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 Example 8.3
Application of Lever Rule
Calculate the amounts of α and L at 1250oC in the Cu-40% Ni alloy.

Example 8.3 SOLUTION Lever Rule:

40  32 45  40
%  *100  61.5 %L  *100  38.5
45  32 45  32
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Section 8.6 Relationship Between Properties and
the Phase Diagram

The mechanical properties of copper-nickel alloys. Copper is strengthened by

up to 60% Ni and nickel is strengthened by up to 40% Cu.

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Section 8.7 Solidification of a Solid-Solution Alloy

The change in structure

of a Cu-40% Ni alloy
during equilibrium
solidification. The nickel
and copper atoms must
diffuse during cooling in
order to satisfy the phase
program and produce a
uniform equilibrium
structure.

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Section 8.8 Fe-Fe3C phase diagram
 Section 8.9 Classification of Steels
Steels can be classified based on their composition or the way they have been
processed.
 Carbon steels contain up to ~2% carbon.
 Decarburized steels contain less than 0.005% C.
 Ultra-low carbon steels contain a maximum of 0.03% carbon.
 They are used for making car bodies and hundreds of other applications.
 Mild steel contains 0.15 to 0.3% carbon.
 This steel is used in buildings, bridges, piping, etc.
 Medium-carbon steels contain 0.3 to 0.6% carbon.
 These are used in making machinery, tractors, mining equipment, etc.
 High-carbon steels contain above 0.6% carbon.
 These are used in making springs, railroad car wheels, and the like.
 Section 8.10 Classification of Cast Irons

 Cast iron - iron-carbon-silicon alloys, typically containing 2–4% C and

0.5–3% Si.

 Types of cast irons:

• Gray cast iron
• White cast iron
• Malleable cast iron
• Ductile or nodular cast iron
• Compacted graphite cast iron