MACHAKOS UNIVERSITY

SCHOOL OF ENGINEERING

DEPARTMENT OF MECHANICAL AND MANUFACTURING ENGINEERING

PROGRAMME:

BSc. MECHANICAL ENGINEERING

UNIT:

EMM221: ENGINEERING MATERIALS

LECTURER:

MR JOHNSON NGUGI

MARCH, 2021

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 LECTURE TWO

Lecture overview

In this lesson, we shall look at important terminology related to the study of equilibrium
phase diagrams and constitutes the first part of the study of iron-carbon (Fe-C) phase
diagram.

This lecture covers:

(i) Lecture objectives

(ii) Lecture notes: Iron Carbon Phase Diagram: Terminology
(iii) Summary of the lecture
(iv) Suggestions for further reading

Lecture Objectives

At the end of this lecture, students should be able to:

(i) Demonstrate understanding of important terminologies used to describe

equilibrium phase diagram.

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1.3. The Iron – Carbon Equilibrium Phase Diagram

1.3.1. Useful Terminology

The following terminologies are foundational to the understanding of the iron-carbon (Fe-C)
equilibrium phase diagram.

(a) Metal alloy

The mechanical properties of metals (such as strength, hardness, toughness and wear resistance)
are usually poor in the pure form of the metals. These properties are improved by the addition of
metals or non-metals to the metal in question. The combination of two or more elements into a
single material (in which the major component is a metal) is termed a metallic alloy.

(b) Phases

A phase is a physically and chemically uniform (or homogeneous) quantity of matter that can be
separated from a nonhomogeneous mixture and that may consist of a single substance or a
mixture of substances. According to this definition, a mixture of ice and water constitutes two
phases. However, a dilute solution of salt in water is a single phase.

(c) Solid Solution

A solid solution is a solid mixture containing a minor component (solute) uniformly distributed
within the crystal lattice of the major component (solvent). A solid solution may take two forms:
substitutional or interstitial. In a substitutional solid solution, atoms of the solute replace those of
the solvent in the latter’s crystal lattice. For this to take place, atoms of the two elements must be
approximately equal in size and have a comparable crystal structure. In an interstitial solid
solution, atoms of the solute (which are comparatively small) occupy the interstice (spaces)
between the atoms of the solvent.

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The bonds in solid solutions are predominantly metallic and the crystal structure remains the
same as that of the solvent.

(d) Intermetallic Compounds

Intermetallic compounds are defined as solid phases involving two or more metallic elements or
a metal and a non-metallic element with an ordered structure and often a well-defined and fixed
stoichiometry. They are hard and brittle with well-defined melting points (solid solutions melt
over a range of temperatures). Bonds in intermetallic compounds may be ionic, covalent,
metallic or mixed.

(e) Solubility limit

For almost all alloy systems, at a specific temperature, a maximum of solute atoms can dissolve
in the solvent phase to form a solid solution. The limit is known as the solubility limit. In
general, solubility limit changes with temperature. If the solute available is more than the
solubility limit that may lead to the formation of different phase, either a solid solution or
compound.

(f) Phase equilibrium

It refers to the set of conditions where more than one phase may exist. In most metallurgical and
materials systems, phase equilibrium involves just solid phases. However, the state of
equilibrium is never completely achieved because of the very slow rate of approach of
equilibrium in solid systems. This leads to a non-equilibrium or meta-stable state, which may
persist indefinitely and of course, has more practical significance than equilibrium phases. An
equilibrium state of the solid system can be reflected in terms of characteristics of the
microstructure, phases present and their compositions, relative phase amounts and their spatial
arrangement or distribution

(g) Variables of a system

These include two external variables namely temperature and pressure along with internal
variables such as composition (C) and the number of phases (P). The number of independent

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variables among these gives the degrees of freedom (F) or variance. All these are related for a
chosen system as follows:

P+ F=C+ 2

This is known as the Gibbs Phase rule. The degrees of freedom cannot be less than zero so that
we have an upper limit to the number of phases that can exist in equilibrium for a given system.
For practical purpose, in the metallurgical and materials field, pressure can be considered as a
constant, and thus the condensed phase rule is given as follows:

P+ F=C+ 1

(h) Equilibrium Phase Diagram

Useful engineering alloys are built from solid solutions and intermetallic compounds. Materials
engineers use phase diagrams to develop these alloys. Equilibrium phase diagrams are charts
showing the relationship between composition, temperature and structure in an alloy system.

They are constructed from cooling curves i.e., the alloying components are melted together in
different proportions and then cooled. For each proportion, the temperature at which
solidification starts, the temperature at which solidification ends, and the composition of the
precipitate are determined.

Figure 1.5 represent a binary phase diagram (a binary phase diagram is a phase diagram of two
components) of metals A and B.

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 Figure 1.5: A binary phase diagram of metals A and B

The x-axis of the phase diagram represents the composition. The composition of metal A is
100% on the extreme left side and decreases to 0% at the other end. The composition of metal B
starts from zero (where A is 100%) to 100% at the other end (where A is 0%). At every point
along the x-axis, the sum of the compositions of A and B is equal to 100%, that is, A% + B% =
100%. The y-axis represents the temperature.

The phases of a phase diagram are usually named using Greek letters from left to right. Single-
phase regions are separated by mixed-phase region. For instance, in Figure 1.1, L and α are
separated by the region (L + α).

The area labelled L (liquid) in Figure 1.1 represent the region where the alloy is in a molten
state. The liquidus is the line (or lines) on a phase diagram above which only liquid is present. A
solidus is a line on a phase diagram below which alloys are completely solid. Alternatively, it is
the highest temperature at which an alloy is solid – where melting begins. A solvus line indicates
the limits of solubility of one solid phase in another.

(i) Invariant Reactions in Phase Diagrams

An invariant reaction in a binary phase diagram occurs when three phases are in equilibrium.

Types of invariant reactions

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Eutectic reaction: A eutectic reaction is a three-phase reaction, by which, on cooling, a liquid
(molten metal in this case) transforms into two solid phases at the same time. A eutectic reaction
is illustrated in Figure 1.1 at point E. Upon solidification at point E (the eutectic temperature),
the liquid transforms into a mixture of two phases, that is α and β. The reaction is reversible and
can be represented as follows:

L ↔α + β

The alloy composition at which the eutectic reaction occurs is called the eutectic composition.

Eutectoid reaction: This reaction is similar to a eutectic reaction. The difference is a solid phase
(rather than a liquid) transforms into a mixture of two solid phases at the eutectoid temperature.
This reaction is also reversible and is represented as follows:

S1 ↔ S2 + S3

A eutectoid reaction is illustrated in Figure 1.6 at point E where, upon cooling, β transforms into
(α + γ), that is:

β ↔ α +γ

Figure 1.6: Eutectoid reaction

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Peritectic reaction: A peritectic reaction is a reaction where a solid phase and liquid phase will
together form a second solid phase at a particular temperature and composition. A peritectic
reaction is represented as follows:

L+ S1 ↔ S2

A peritectic reaction is shown in Figure 1.7 whereby the (L + α) transforms to β at the peritectic
composition, that is:

L+α ↔ β

Figure 1.7: Peritectic reaction

Summary

In this lesson, we looked at several important terminologies used to describe equilibrium

phase diagrams. Knowledge of these terminologies is key to the understanding of the Fe-C
phase diagram which will be considered in the next lecture.

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Further Reading

1. Rading, G.O., Concise Notes on Materials Science and Engineering, Trafford

Publishing, Victoria, CA, 2007.