Introduction

Phase diagram for pure water 2

WHY STUDY PHASE EQUILIBRIA?

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Why study phase equilibria?

Some properties of materials are functions of their

microstructures.
 These microstructures can be altered by
thermal treatment.
 For example, steel alloys undergo phase
transformations at various temperatures,
resulting in different mechanical properties.
We can take advantage of these phase changes to
create materials with desired properties.

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 Why study phase equilibria?
Heat Treatment of
Materials

Phase Changes

Microstructure

Mechanical Properties of Materials

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This Photo by Unknown Author is licensed under CC BY-SA-NC
Phase Definition

Phase
 Homogeneous portion of a system that has uniform
physical and chemical characteristics
 A single-phase material is one that has the same
composition and structure at every point.
 Every pure material is considered to be a phase; so
also is every solid, liquid, and gaseous solution.

vs
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Phase Definition

 Each phase will have its own

distinct properties
 A boundary separating the
phases will exist across
 A discontinuous and abrupt
change in physical and/or
chemical characteristics will
occur across the boundary.

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Phase vs Component
 Pure FCC Al is a single-component (Al), single-phase
(FCC) system.
 A mixture of pure ice and pure water is a single-
component (H2O) system composed of two phases.

Single component in two phases

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Phase vs Component
 A mixture of BCC iron and FCC iron is also a single-
component system composed of two phases.
 A solid solution of Cu and Ni is a two-component single-
phase system (since Cu and Ni are soluble in each
other).

This Photo by Unknown Author is licensed under CC BY-SA 9

Microstructure and Phase
In metal alloys, the microstructure is characterized by
 the number of phases present,

 the relative proportion of these phases, and

 the manner in which the phases are distributed or

arranged.

Microstructure of a lead tin

alloy (50 wt% Sn – 50 wt% Pb)

Lead rich -phase (dark)

Tin rich -phase (light) 10
Microstructure and Phase
In metal alloys, the microstructure depends on variables
such as
 the alloying elements present,

 the concentration of the alloying elements, and

 the heat treatment of the alloy

 i.e., the temperature, the heating time at the

elevated temperature, the rate of cooling to room
temperature

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Phase Equilibrium
 It refers to the state of a system in which the phase
characteristics remain constant over indefinite periods
of time.
 A system at equilibrium is a system in its most stable
state.
 At equilibrium, the free energy of the system is a
minimum for some set combination of temperature,
pressure, and composition.

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Phase Equilibria

 In solid solution systems, a state of equilibrium

is never fully reached because the rate of
approach to equilibrium is extremely slow.
 Such systems are said to be in a metastable
state.
 A metastable state or microstructure may
persist indefinitely, experiencing only extremely
slight and almost imperceptible changes as
time progresses.

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Phase Equilibria
Often, metastable structures are of more practical
importance than equilibrium ones.
 For example, some steel and aluminum
alloys rely for their strength on the
development of metastable microstructures
during carefully designed heat treatments.

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Phase Diagram

 a graphical representation of the phase present in

a compound and the
 Includes material composition, temperature and
pressure over which the phases are stable
 also called an equilibrium diagram

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One-Component Phase Diagram

 Also called a unary phase

diagram
 Also called a pressure-
temperature (P-T)
diagram
 The composition is held
constant (i.e., the system
is a pure substance)
 Least complex class of
phase diagram

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Phase Diagram for Water
 The phase diagram is composed of regions of pressure
and temperature where only a single phase is stable.
 Note that if the pressure and temperature are specified,
the equilibrium state of the system is established.

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Phase Diagram for Water

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Phase Diagram for Water

Phase Boundaries

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Phase Diagram for Water

Invariant Point
(Triple Point)

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Invariant/Triple Point
On the water phase diagram, three-phase equilibrium
occurs at a fixed temperature and pressure.
 Equilibrium in which there is no freedom to change
variables is called invariant.
 The invariant point for water, as mentioned
previously, is also called a triple point, since three
phases are in equilibrium.

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Binary Phase Diagrams

These are maps that represent the relationships

between temperature and the compositions and
quantities of phases at equilibrium.

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Binary Phase Diagrams
 Pressure is held constant while temperature and
composition may vary

Copper – Nickel Phase diagram 23

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Solubility of sugar (C12H22O11) in a sugar-water syrup
Binary Phase Diagrams

Many microstructures develop from phase

transformations that occur when the temperature is
altered (such as in cooling).

 Transition from one phase to another

 The appearance or disappearance of a phase.

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Solubility Limit
 For many alloy systems and at some specific
temperature, there is a maximum concentration of solute
atoms that may dissolve in the solvent to form a solid
solution.
 This is called the solubility limit.

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Binary Phase Systems
There are several types:
 Isomorphous

 Eutectic

 Eutectoid

 Peritectic

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Binary Isomorphous Systems
 The simplest two-component system.
 Complete solubility occurs over the entire
composition range in both the liquid and solid
states.
 This behavior is characterized as “isomorphous”.

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Binary Isomorphous Systems

The lines created in this way are called phase

boundaries, and the areas enclosed by these lines
are called phase fields.

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Binary Isomorphous Systems
 For metallic alloys, solid solutions are commonly
designated by lowercase Greek letters (, , ,
etc.).
 The phase boundary separating the single-phase
liquid region from the two-phase (solid+liquid)
region is called a liquidus boundary.
 The phase boundary separating the two-phase
(solid+liquid) region from the single-phase solid
region is called a solidus boundary.

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The Copper Nickel System
 Nickel and copper are mutually soluble in each other
in the solid state for all compositions because
 Both Cu and Ni have an FCC structure

 Both have nearly identical atomic radii

 Both have nearly identical electronegativities

 Both have similar valences

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 Binary Phase Diagrams

Important aspects:
Copper – Nickel Phase diagram  liquidus and solidus line
 melting points
 phase boundaries 32
 Binary Phase Diagrams

Melting Points

Copper – Nickel Phase diagram

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Melting Points
 For a binary isomorphous system, the solidus
and liquidus lines intersect at the two
composition extremities, corresponding to the
melting temperatures of the pure components.
 For any composition other than pure
components, melting occurs over a range of
temperatures between the solidus and liquidus
lines.

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Binary Phase Diagrams
Determining Compositions

Pure  phase
Copper – Nickel Phase diagram 60% Ni, 40% Cu
Solid solution
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Binary Phase Diagrams
Determining Compositions

 + L phase
35% Ni, 65% Cu

Copper – Nickel Phase diagram

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Binary Phase Diagrams
Determining Compositions

Phase compositions for

 and L can be obtained
by creating a tie-line
Copper – Nickel Phase diagram across the point

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Binary Phase Diagrams
Determining Compositions

The composition of -
phase is 42.5 wt % Ni
– 57.5 wt % Cu

Copper – Nickel Phase diagram

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Binary Phase Diagrams
Determining Compositions

The composition of L-
phase is 31.5 wt % Ni
– 68.5 wt % Cu

Copper – Nickel Phase diagram

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Binary Phase Diagrams
Determining Compositions

Phase amounts can be

obtained using the
inverse lever arm rule
Copper – Nickel Phase diagram

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Binary Phase Diagrams
Determining Compositions

Copper – Nickel Phase diagram

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Binary Phase Diagrams
Determining Compositions

Copper – Nickel Phase diagram

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Determination of Phase
Composition
 If only one phase is present, the composition of
the phase is the same as the overall
composition of the alloy.
 For an alloy having composition and
temperature located in a two-phase region, tie
lines are used to determine the phase
composition.

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 Concept Check!
If a copper-nickel alloy of 70 wt%
Ni – 30 wt% Cu is slowly heated
from 1300 C

• At what temperature does the

first liquid phase form?
• What is the composition of this
liquid phase
• At what temperature does
complete melting of the alloy
occur?
• What is the composition of the
last solid remaining prior to
complete melting?
Copper – Nickel Phase diagram

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 Concept Check!
Is it possible to have a copper-
nickel alloy that at equilibrium
consist of an -phase of
composition 37wt% Ni – 63wt%
Cu, and also a liquid phase of
composition 20wt% Ni – 80 wt%
Cu?
If yes, what will be the
approximate temperature of the
alloy? If no, why is it not possible?

Copper – Nickel Phase diagram

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Concept Check!
A solid solution consists of a liquid phase (L) and a solid
phase (). The overall composition of the solid solution is
45% A and 55% B. The liquid phase is composed of 10% A
and 90% B. The solid phase is composed of 60% A and
40% B. All percentages are weight percentages.
(1) How much liquid phase is present?
(2) How much solid phase is present?

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