MATERIAL SCIENCE

MODULE III
SOLID SOLUTIONS

Chapter II – Phase Diagrams

 Phase Diagrams

Phase diagrams , are also known as

Equilibrium/Constitutional Diagrams , are a very
important tool used in the study of alloys.

A phase diagram consists of two parameters –

temperature , taken on the ordinate and the
alloy composition taken on the abscissa.

Ideally the phase diagram will show the phase

relationship under equilibrium conditions, in
which there is no change with time.

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Role / Importance / Objectives of the phase diagram :
1. Shows the phases in equilibrium for a given allow composition, at a glance.
Equilibrium refers to the state of balance which exists, or which tends to be attained, between the phases
in the structure of an alloy after a physical or chemical change has taken place.
2. Shows the relationship between the composition , temperature, and alloy structure in series.
3. Permits to study and control processes such as
 Phase separation ,
 Solidification of metals and alloys ,
 Purification of materials ,
 The growth and doping single crystals, and
 The structural changes produced by heat treatment ,casting ,etc.

4. Provides the knowledge of phase composition and phase stability as a function of temperature,
pressure and composition.
5. Marks Liquidus (i.e., the lines or surfaces in an equilibrium dia. Indicating temperature of beginning of
solidification or completion of melting) and Solidus (i.e., the lines or surfaces in an equilibrium dia.
Indicating temperature of completion of solidification or beginning of melting)

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Phase Diagrams are classified as
i. Unary (or one component) phase diagram plotted as pressure on the vertical axis and
temperature on the horizontal axis.
ii. Binary (or two component) phase diagram which finds extensive uses.
iii. Ternary (or three component) phase diagram.

▪ Equilibrium conditions may be approached by extremely slow heating and cooling so that if a
phase change is to occur, sufficient time is allowed.
▪ Under welding and casting conditions equilibrium conditions are not obtained.
This limits the field of use of equilibrium diagrams; however they assist to some extent in
predicting the phase relations, compositional changes and structures in the systems not at
equilibrium.

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 Systems, Phases and Structural Constituents

1. System:
A system is a substance (or group of substances) so isolated from its surrounding that it is
unaffected by these and is subjected to changes in overall composition, temperature, pressure or
total volume only to the extent allowed by investigator.
A system may be composed of gases, liquids, solids or any combination of them and may involve
metals and non-metals, either separately or in combination.
An alloy system is combination of two or more elements, forming alloys which are considered
within a specified range of temperature, pressure and concentration.
A system is classified according to number of components that constitute the system.
A system having one component is Unary system, and having two, three and four components are
known as Binary, Ternary, and Quaternary systems, respectively.

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2. Phases:

In an alloy system, the components may combine (within a certain temperature range) to form two
homogeneous coexisting portions, each portion having different composition and properties. For
example, a liquid (portion) may exist in equilibrium with a solid solution (portion).

These homogeneous, physically distinct portions of the system are called Phases. In above
example liquid is one phase and solid is another.

A phase may be defined as any part or portion of a chemical system which posses distinctive
physical characteristics, is limited by definite bonding surfaces, and may conceivably be
mechanically separated from its surroundings.

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3. Structural Constituents:
The phases in alloy are not necessarily uniformly distributed throughout the structure. There are
certain ways in which these phases may be associated to form the structure.
The association of phases in a recognizably distinct fashion may be referred to as a structural
constituent of the alloy.
It is customary to call those parts of the microstructure that have a clearly identifiable
appearance under the microscope, the constituents of the structure.
For example,
i. A Eutectic is a structural constituent of the alloy.
ii. Pearlite, Martensite and Sorbite are microconstituents in steel.

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 Phase rules / Interpretation of Phase Diagrams

The following three useful conclusions are the rules necessary for interpreting phase diagrams

I. The phases that are present / Prediction of Phase

II. The chemical composition of each phase / Phase Composition

III. The amount of each phase / Lever Rule

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 Rule I – Prediction of Phases
▪ From a phase diagram, specific information can be obtained only if a temperature and a
composition is specified.
▪ This can be done by using both temperature and composition parameters to identify the point on
the phase diagram. Once done, depending on its location, identify the phase present at that
particular point.
▪ For example, the state of the alloy of composition 30% Bismuth can be determined only with
reference to a certain temperature. Thus when the alloy is at 1200ºF, point 1 is located and at 900ºF
and 600ºF, points 2 and 3 are located respectively.
▪ The next step is to determine the phase or phases present at 1,2, and, 3.
1. With 30% Bi – 70% Sb alloy at 1200ºF, only one phase, i.e., the liquid solution is present.
2. With the same alloy but at 900ºF, two phases are present, i.e., liquid solution and solid
solution.
3. With the same alloy but at 600ºF, only one phase, i.e., solid solution is present.
Similar analysis can be done for any other alloy composition and temperature in phase diagram.
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 Rule II – Phase Composition

▪ To find out the composition of phases which are stable at a given temperature (say 900 ºF) draw a
horizontal line (isothermal line), OP at the given temperature.

▪ The projections of the intersections of the isothermal line with the solidus and liquidus
respectively, give the compositions of the solid and liquid, which co-exist in equilibrium at that
temperature.

▪ For example-
1. Liquid phase, point P has the composition roughly 62% Bismuth.
2. Solid phase, point O has the composition roughly 14% Bismuth.

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 Rule III – Lever Arm Principle

▪ Besides indicating the number of phases and phase composition , the phase diagram also tells
the proportion of co-existing phases at a given temperature.
▪ To determine the relative amount of the two phases , erect an ordinate at a point (30% Bi) on
the scale which gives the total or overall composition of the alloy.
▪ The intersection of this line AL and given isothermal line OP i.e., point M, is the fulcrum of a
simple lever system and OM and MP are two lever arms. The relative length of lever arms
multiplied by amounts of the phase present must balance.
▪ The proportion of solid corresponds to the length of segment adjacent to liquidus line,
whereas proportion of liquid corresponds to the length of segment adjacent to solidus line.
▪ This is called lever rule because the amount of a given phase multiplied by its lever arm is
equal to the amount of the other phase multiplied by its arm.
▪ The isothermal line is also referred to as the Tie line since it joins the composition of the two
phases in equilibrium at a specific temperature.
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▪  

When expressed mathematically it gives us the following :

1.The amount of solid phase i.e.

2.The amount of liquid phase i.e.

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 Gibbs Phase Rule
The phase rule, also known as the Gibbs Phase Rule, establishes the relationship between the
number of degrees of freedom (F),the number of components(C) and the number of phases(P).
It is mathematically expressed as follows :
P+F=C+2
P - Number of phases (Solid or liquid and so on) ;
F - Number of degrees of freedom (pressure ,temperature ,concentration and so on) without altering
the equilibrium
C - Number of Components n the system (For example Pb-Sn)
In metallurgical systems the pressure is regarded as remaining fixed at one atm and hence the
pressure variation is neglected.
It is used while dealing with multicomponent systems to determine whether the microstructures are
in equilibrium or not.

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Phase rule helps to determine maximum number of phase present in an alloy system under
equilibrium conditions at any point in phase diagram.

The phase rule can also be used to determine the degree of freedom that can be changed.

Consider point X and Y in the figure, it is required to determine degree of freedom using phase
rule.
1. Point X, C = 2, P = 1
Applying the rule, F = C+2-P = 2+2-1 = 3 degrees of freedom.
2. Point Y, C = 2, P = 2
Applying the rule, F = 2+2-2 = 2 degrees of freedom.

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 Assignment

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 Cooling Curves

A method, to determine the temperatures at which phase changes occur in an alloy system,
consists of temperature as a function of time.

Method is useful in,

Studying the changes that occur during the solidification of alloys, and

Determining transformations subsequent to solidification.

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 Cooling Curves for Pure Metals or Compound
▪ Liquid metal cools from A to B. First crystal begin
to form at point B.
▪ From B to C, the melt liberates latent heat of
fusion in such amounts that the temperature from
B to C remains constant, until whole mass is
solidified. Between B and C, mass is partially
Possible liquid and partly solid.
undercooling
▪ On further cooling from C to D, the solid metal
cools and tends to reach room temperature.
▪ Slopes of AB and CD depends upon the specific
heats of liquid and solid metals respectively.
Real
cooling ▪ Real cooling curve - Once the process initiates the
curve latent heat that is released by the metal raises the
temperature back to its melting point. Thereafter the
temperature remains constant till the solidification is
complete.
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 Cooling Curve for Pure Iron

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 Cooling Curves for a Binary Solid Solution

▪ In binary system during freezing period, the

temperature does not remain constant, rather it
drops along a line till the whole mass is solid.

▪ The dropping trend indicates that the alloy does

not solidify at constant temperature, rather it
posses a freezing range which is due to changes in
composition of solid and liquid phases.

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 Cooling Curves for a Binary Eutectic System
▪ In this system the two components are
completely soluble in the liquid state but
entirely insoluble in solid state.
▪ Liquid cools along UV until temperature V is
reached.
▪ At V, one component that is in excess will
crystallize and temperature will drop along
VW.
▪ At W, the liquid composition has been
reached at which the two components
crystallize simultaneously from the solution.
The temperature remains constant until the
whole mass is solid.
▪ Cooling from X to Y is usual.

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 Series of cooling curves

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▪ Two metals of binary solid solution system are mixed in different portions, melted and
then cooled, and a cooling curve is constructed for each composition.

▪ The phase diagram shows two distinct phases; one is liquid metal solution and the
other is solid solution.

▪ If in a phase diagram, for each changes of phase, adequate time is allowed for the
change to complete so that phase change takes place under equilibrium conditions, the
phase diagram will be known as equilibrium phase diagram.

▪ Generally, equilibrium conditions are not attained during the solidification of weld and
casting, that results in porous, cored material which is usually of very inhomogeneous
composition.

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