Lecture 7: Phase Diagrams

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 Alloys
Introduction to Materials Science, Chapter 9, Phase Diagrams

Slow cooling

Fast cooling

Microstructure of Steel
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 Phase Diagrams
• Understanding of phase diagrams for alloy systems is
extremely important because there is a strong
correlation between microstructure and mechanical
properties,
• Development of microstructure of an alloy is related
to the characteristics of its phase diagram.
• In addition, phase diagrams provide valuable
information about melting, casting, crystallization,
and other phenomena.

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 Chapter Outline: Phase Diagrams
Microstructure + Phase Transformations
in Multicomponent Systems

 Definitions and basic concepts

 Phases and microstructure
 Binary isomorphous systems (complete solid solubility)
 Binary eutectic systems (limited solid solubility)
 Binary systems with intermediate phases/compounds
 The iron-carbon system (steel and cast iron)

Not tested: The Gibbs Phase Rule

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 Components and Phases
Component - chemical species
(Fe + C in steel; H2O + NaCl in salt water).
Binary alloy 2 two components,
Ternary alloy – 3, etc.

Phase – a portion with distinct, uniform physical or

chemical characteristics

Single-phase system: Homogeneous.

Two or more phases
Mixture or Heterogeneous system.
e.g. water + ice, separated by a phase boundary
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 Solubility Limit
Solvent - host or major component
Solute - minor component (Chapter 4).

Solubility Limit = maximum amount that can be dissolved

in a phase
(e.g. alcohol has unlimited solubility in water, sugar has
a limited solubility, oil is insoluble).

Same concepts for solids: Cu and Ni are mutually soluble

in any amount (unlimited solid solubility), while C has a
limited solubility in Fe.
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Solubility of Sugar in Water

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 Microstructure
Properties of an alloy depend on proportions of the phases and on
how they are arranged at the microscopic level.
Microstructure: number of phases, their proportions, and their
arrangements
Microstructure of cast Iron

Alloy of Fe with 4 wt.% C. There are several phases. The long gray
regions are flakes of graphite. The matrix is a fine mixture of BCC
Fe and Fe3C compound.
Phase diagrams help understand and predict microstructures 8
 Equilibrium and Metastable States
Equilibrium: at constant temperature, pressure and
composition system is stable
(Equilibrium is achieved given sufficient time, but that may be
very long. )
Metastable: System appears to be stable

Equilibrium  minimum in the free energy.

• Under conditions of constant temperature, pressure and
composition, change is toward lower free energy.
• Stable equilibrium is state with equilibrium

Free Energy
minimum free energy.
• Metastable state is a local minimum
of free energy. metastable
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 Phase diagram
Phase diagram - combinations of temperature, pressure or composition for
which specific phases exist at equilibrium

H2O: diagram shows temperature and pressure at which ice (solid),water

(liquid) and steam (gas) exist.

Pressure–temperature phase
diagram for Intersection of
the dashed horizontal line at
1 atm pressure with
the solid-liquid phase
boundary (point 2)
corresponds to the
melting point at this pressure
(T= 0 C ). Similarly, point 3,
the
intersection with the liquid-
vapor boundary, represents
the boiling
point (T =100C).

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 Phase diagram
Show what phases exist at equilibrium and what
transformations we can expect when we change T,
P, or composition

Consider binary alloys only

Pressure constant at one atmosphere.

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 Binary Isomorphous System (I)
Assume Complete Solubility

L
+L

Three phases :
Liquid (L) , solid + liquid (+L), solid ()
Liquidus line separates liquid from liquid + solid
Solidus line separates solid from liquid + solid 12
 Introduction to Materials Science, Chapter 9, Phase Diagrams

Binary Isomorphous System (III)

One-component: melting occurs at a well-defined temperature.
Multi-component: melting occurs over range of temperatures
between solidus and liquidus lines.
Solid and liquid phases are in equilibrium in this temperature range.

L Liquid solution
+L

Liquid solution
 +
Crystallites of
Solid solution
Polycrystal
Solid solution

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 Interpretation of Phase Diagrams
Given:
temperature + composition  determine
1) Phases present
2) Compositions of phases
3) Relative fractions of phases
Composition in a two phase region:
1. Locate composition and temperature
2. Draw tie line or isotherm
3. Note intersection with phase boundaries
4. Read compositions at the intersections
Liquid and solid phases have these compositions
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 The Lever Rule
Amounts of each phase in two phase region
Locate composition and temperature
Draw tie line or isotherm
Fraction of a phase = length of tie line to other phase
boundary divided by the length of tie line

The lever rule is a mechanical analogy to

the mass balance calculation. The tie line
in the two-phase region is analogous to a
lever balanced on a fulcrum.

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 Introduction to Materials Science, Chapter 9, Phase Diagrams

The Lever Rule

Mass fractions: WL = S / (R+S) = (C- Co) / (C - CL)

W = R / (R+S) = (Co- CL) / (C - CL)

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 Introduction to Materials Science, Chapter 9, Phase Diagrams

Derivation of the lever rule

W and WL are fractions of  and L phases

1) All material is in one phase or the other:

W + WL = 1
2) Composition equal composition in one phase +
composition second phase
at given T:
Co = WC + WLCL

3) Solution gives Lever rule.

WL = (C- Co) / (C - CL)
W = (Co- CL) / (C - CL)
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 Phase compositions and amounts. An example.

Co = 35 wt. %, CL = 31.5 wt. %, C = 42.5 wt. %

Mass fractions: WL = (C- Co) / (C - CL) = 0.68
W = (Co- CL) / (C - CL) = 0.32
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 Introduction to Materials Science, Chapter 9, Phase Diagrams

Binary Isomorphous Systems (II)

Cu-Ni
Complete solubility occurs because Cu and Ni have the same crystal
structure (FCC), similar radii, electronegativity and valence

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Microstructure in binary isomorphous alloys
Equilibrium (very slow) cooling

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 Introduction to Materials Science, Chapter 9, Phase Diagrams

MECHANICAL PROPERTIES OF ISOMORPHOUS ALLOYS

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 Introduction to Materials Science, Chapter 9, Phase Diagrams
1. A 50 wt% Ni–50 wt%
Cu alloy is slowly cooled
from (1400 °C ) to
(1200 °C ).
(a) At what temperature
does the first solid phase
form?
(b) What is the
composition of this solid
phase?
(c) At what temperature
does the liquid solidify?
(d) What is the
composition of this last
remaining liquid phase?
(e) What is the fraction of
both solid and liquid
phases

Ans: (a)1320 °C, (b) Cά=62 wt% , (c) = 1270 °C, (d) CL =37 wt%

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 Introduction to Materials Science, Chapter 9, Phase Diagrams

2. A 65 wt% Ni–35
wt% Cu alloy is heated
to a temperature within
the ά+liquid-phase
region. If the
composition of the ά -
phase is 70 wt% Ni,
determine:
(a) The temperature
of the alloy
(b) The composition of
the liquid phase
(c) The mass fractions
of both phases

Ans: (a)1340 °C, (b) CL =59 wt% (c) Wά= 0.55 , WL = 0.45

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