Lecture: 10

ME 2203 Engineering Materials

Topic: Phase Diagrams
Materials Science and Engineering, WD Callister, Jr. and DG Rethwisch, 8th
Edition, SI Version, John Wiley and Sons, 2011 (Chapter 9)

Dr. Kazi Md. Shorowordi

Department of MME
Bangladesh University of Engineering and Technology, Dhaka - 1000
 PHASES AND THE PHASE DIAGRAM
• Pure metallic elements have engineering applications; for
example, ultra-high purity copper (Cu) or aluminium (Al) is used
to make microelectronic circuitry.

• In most applications, however, we use alloys.

– We define an “alloy” as a material that exhibits properties of a metallic
material and is made from multiple elements.
– A plain carbon steel is an alloy of iron (Fe) and carbon (C).
– Corrosion-resistant stainless steels are alloys that usually contain iron
(Fe), carbon (C), chromium (Cr), nickel (Ni), and some other elements.
– Similarly, there are alloys based on aluminium (Al), copper (Cu), cobalt
(Co), nickel (Ni), titanium (Ti), zinc (Zn), and zirconium (Zr).

• There are two types of alloys: single-phase alloys and multiple

phase alloys.

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Phase
• A phase may be defined as a homogeneous portion of a system that has uniform physical and
chemical characteristics.

• Every pure material is considered to be a phase; so also is every solid, liquid, and gaseous
solution.

• For example, the sugar–water syrup solution is one phase, and solid sugar is another.
– Each has different physical properties (one is a liquid, the other is a solid);
– furthermore, each is different chemically (i.e., has a different chemical composition);
– one is virtually pure sugar, the other is a solution of H2O and C12H22O11.

• If more than one phase is present in a given system, each will have its own distinct properties,
and a boundary separating the phases will exist across which there will be a discontinuous
and abrupt change in physical and/or chemical characteristics.

• When two phases are present in a system, it is not necessary that there be a difference in
both physical and chemical properties;
– a disparity in one or the other set of properties is sufficient.
– When water and ice are present in a container, two separate phases exist; they are physically dissimilar (one
is a solid, the other is a liquid) but identical in chemical makeup.

• Also, when a substance can exist in two or more polymorphic forms (e.g., having both FCC and
BCC structures), each of these structures is a separate phase because their respective physical
characteristics differ.
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• A phase has the following characteristics:
1. the same structure or atomic arrangement throughout;

2. roughly the same composition and properties throughout; and

3. a definite interface between the phase and any surrounding or adjoining phases.

• For example, if we enclose a block of ice in a vacuum chamber [Figure

(a)],
– the ice begins to melt, and some of the water vapourizes.

– Under these conditions, we have three phases coexisting: solid H2O, liquid H2O,
and gaseous H2O.

– Each of these forms of H2O is a distinct phase; each has a unique atomic
arrangement, unique properties, and a definite boundary between each form.

– In this case, the phases have identical compositions.

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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. 5
 PHASE RULE
• Josiah Willard Gibbs (1839–1903) was a brilliant American physicist
and mathematician who conducted some of the most important
pioneering work related to thermodynamic equilibrium.

• Gibbs developed the phase rule in 1875–1876.

• It describes the relationship between the number of components and
the number of phases for a given system and the conditions that may
be allowed to change (e.g., temperature, pressure, etc.).

• It has the general form:  P + F = C + N Details of Phase Rule

will be taught later.
• In the phase rule,
– C is the number of chemically independent components, usually elements or
compounds, in the system;
– F is the number of degrees of freedom, or the number of variables (such as
temperature, pressure, or composition), that are allowed to change
independently without changing the number of phases in equilibrium;
– P is the number of phases present (please do not confuse P with “pressure”);
– N is the number of noncompositional variables (e.g., temperature and pressure).
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• It is important to note that the Gibbs phase rule assumes
thermodynamic equilibrium and, more often than not in
materials processing, we encounter conditions in which
equilibrium is not maintained.
– Therefore, you should not be surprised to see that the number and
compositions of phases seen in practice are dramatically different
from those predicted by the Gibbs phase rule.

• Another point to note is that phases do not always have to

be solid, liquid, and gaseous forms of a material.
– An element, such as iron (Fe), can exist in FCC and BCC crystal
structures.
– These two solid forms of iron are two different phases of iron that
will be stable at different temperatures and pressure conditions.

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Example:
• As an example of the use of the phase rule, let’s consider the case of pure
magnesium (Mg).

• Figure in the following page shows a unary (C = 1) phase diagram in which the lines
divide the liquid, solid, and vapour phases.
– This unary phase diagram is also called a pressure-temperature or P-T diagram.

• In the unary phase diagram, there is only one component;

– in this case, magnesium (Mg).

• Depending on the temperature and pressure, however, there may be one, two, or
even three phases present at any one time: solid magnesium, liquid magnesium, and
magnesium vapour.

• Note that at atmospheric pressure (one atmosphere, given by the dashed line),
– the intersection of the lines in the phase diagram give the usual melting and boiling
temperatures for magnesium.

– At very low pressures, a solid such as magnesium (Mg) can sublime, or go directly to a vapour
form without melting, when it is heated.

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Schematic unary phase diagram for magnesium, showing the melting and
boiling temperatures at one atmosphere pressure.
On this diagram, point X is the triple point. 9
• Suppose we have a pressure and temperature that put us at point A in the
phase diagram.

• At this point, magnesium is all liquid.

• The number of phases is one (liquid).

• The phase rule tells us that there are two degrees of freedom.

• From Phase Rule:

– 2+C=F+P 2+1=F+1 F=2

What does this mean?

Within limits, as seen in Figure, we can change the pressure the temperature, or both, and
still be in an all-liquid portion of the diagram.

Put another way, we must fix both the temperature and the pressure to know precisely where
we are in the liquid portion of the diagram. 10
• Consider point B, the boundary between the solid and liquid
portions of the diagram.

• The number of components, C, is still one, but at point B, the

solid and liquid coexist, or the number of phases P is two.

• From the Phase Rule,

– 2+C=F+P  2 + 1 = F + 2  F = 1  ONLY ONE DOF

If we change the temperature, the pressure must also be adjusted if

we are to stay on the boundary where the liquid and solid coexist.

On the other hand, if we fix the pressure, the phase diagram tells us
the temperature that we must have if solid and liquid are to coexist.
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• Finally, at point X, solid, liquid, and vapour coexist. While
the number of components is still one, there are three
phases.

• The number of degrees of freedom is zero:

– 2+C=F+P 2+1=F+3 F=0  DOF=zero

Now we have no degrees of freedom; all three phases coexist only if

both the temperature and the pressure are fixed.

A point on the phase diagram at which the solid, liquid, and gaseous
phases coexist under equilibrium conditions is the triple point.
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 DEFINITIONS AND BASIC CONCEPTS
Component
• Components are pure metals and/or compounds of which an alloy is composed.
– For example, in a copper–zinc brass, the components are Cu and Zn.

Solvent
• Represents the element or compound that is present in the greatest amount; on
occasion, solvent atoms are also called host atoms.

Solute
• is used to denote an element or compound present in a minor concentration.

System
• may refer to a specific body of material under consideration (e.g., a ladle of molten
steel).

• Or it may relate to the series of possible alloys consisting of the same components,
but without regard to alloy composition (e.g., the iron–carbon system).

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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 a solubility limit.

• The addition of solute in excess of this solubility limit results

in the formation of another solid solution or compound
– that has a distinctly different composition.

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• For example, at 20C the maximum solubility of sugar in water is 65 wt%.

• As Figure 9.1 indicates, the solubility limit increases slightly with rising temperature.

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MICROSTRUCTURE
• In metal alloys, microstructure is characterized by the
number of phases present, their proportions, and the
manner in which they are distributed or arranged.

• The microstructure of an alloy depends on such variables as

the alloying elements present, their concentrations, and the
heat treatment of the alloy (i.e., the temperature, the
heating time at temperature, and the rate of cooling to
room temperature).

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 PHASE EQUILIBRIA
• Equilibrium is another essential concept that is best described in terms of a
thermodynamic quantity called the free energy.

• In brief, free energy is a function of the internal energy of a system, and also
the randomness or disorder of the atoms or molecules (or entropy).

• A system is at equilibrium
– if its free energy is at a minimum under some specified combination of temperature,
pressure, and composition.

• In a macroscopic sense,
– this means that the characteristics of the system do not change with time but persist
indefinitely;
– that is, the system is stable.

• A change in temperature, pressure, and/or composition for a system in

equilibrium will result in
– an increase in the free energy
– and in a possible spontaneous change to another state whereby the free energy is
lowered. 17
• The term phase equilibrium refers to equilibrium as it applies to
systems in which more than one phase may exist.

Example:
• A sugar–water syrup is contained in a closed vessel and the
solution is in contact with solid sugar at 20C.
– If the system is at equilibrium, the composition of the syrup is 65 wt%
and C12H22O11-35 wt% H2O (Figure 9.1), and the amounts and
compositions of the syrup and solid sugar will remain constant with time.

– If the temperature of the system is suddenly raised to 100C, this

equilibrium or balance is temporarily upset in that the solubility limit has
been increased to 80 wt% C12H22O11 (Figure 9.1).

– Thus, some of the solid sugar will go into solution in the syrup.
• This will continue until the new equilibrium syrup concentration is established at
the higher temperature.

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ONE-COMPONENT (OR UNARY) PHASE DIAGRAMS

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