PHASE DIAGRAMS

Introduction
 Phase diagrams (PD), also known as equilibrium diagrams or constitutional
diagrams are a very important tool in the study of alloys. An alloy is a
substance that consists of two or more chemical elements, in which the
metallic atoms predominate and the metallic bond predominates in the solid
solution.
 A phase diagram has temperature as its ordinate and composition (alloy) as
abscissa, which gives the relationship between the composition, temperature
and structure of an alloy in series
 In general, the understanding of the phase diagrams for alloy system is
extremely important because there is a strong correlation between
microstructure and properties, and the development of microstructure of an
alloy is related to the characteristics of its phase diagram.

Phase diagram classification

1. unary
2. binary
3. ternary
Based on the components (materials) the classification is made. It is noted that the
PD are obtained for these combination under equilibrium conditions that means by
extremely slow heating and cooling so that if a phase change is to occur, sufficient
time is allowed.
 Below classification is according to the relation of the components in the liquid
and solid states
1. components completely soluble in the liquid state
 completely soluble in the solid state
 insoluble in the solid state: the eutectic reaction

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  partly soluble in the solid state: the eutectic reaction
 formation of a congruent-melting intermediate phase
 the peritectic reaction
2. components partly soluble in the liquid state: the monotectic reaction
3. components insoluble in the liquid state and insoluble in the solid state
4. transformations in the solid state
 Allotropic change
 Order-disorder
 The eutectoid reaction
 The peritectoid reaction

Method of construction of phase diagrams:

Cooling curve:
A method to obtain the temperatures at which phase changes (liquid ↔ solid)
occur in an alloys system. The cooling curve is drawn for the temperature as a
function of time. The below figure is shown for different alloy system which are
assumed to be slowly cooled, the resulting curve is called cooling curve.

Figure 1: a, b, c represents three different types of cooling curves

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(a) Cooling curve of pure metal or compound
 Liquid metal cools from P to Q. First crystals begin to form at point Q.
From Q to R, the melt liberates latent heat of fusion in such amounts that
the temp from Q to R remains constant, until the whole mass has entirely
solidified at point R. Between Q and R, the mass is partly liquid and partly
solid.
 On further cooling from R to S, the solid metal cools and tends to reach
room temp.
(b) Cooling curve of a binary solid solution (isomorphous alloy system)
 Curve portion PQ is similar, no matter it is for a pure metal or for a binary
system. However, in a binary system, during freezing (ie. QR) period, the
temp does not remain constant, rather it drops along line QR, till the whole
mass is solid at point R.
 The dropping trend of QR indicates that the alloy does not solidify at
constant temp; rather, it possesses a freezing range which is due to the
changes in the composition of the solid and liquid phases which naturally
result in variable freezing/melting points.
(c) Cooling curve of a binary eutectic system
 In this system, the two components are completely soluble in the liquid
state but entirely insoluble in the solid state. Of course PQ is same that for
this case too, but at Q, one component that is in excess will crystallize and
the temperature will drop along QR.
 At point R the liquid composition has been reached at which the two
components crystallize simultaneously from the solution, the temp remains
constant until the whole mass is solid. Cooling from S to T is as usual.
Phase diagram:
 The phase diagram is constructed for binary solid solution or isomorphous
alloy systems, where both the constituents are completely soluble in both

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 liquid and solid state. Few example for such systems are Ni-Cu, Au-Ag, Cr-
Mo and W-Mo etc.
 In two metals of a binary solid solution, such as Cu-Ni system are mixed in
different proportions, melted and then cooled and a cooling curve is
constructed for each composition shown in figure 2

Fig 2. Series of cooling curve giving rise to a phase diagram

 The resulting diagram obtained by joining points Q1, Q2, …. and R1, R2
R3…, will be the phase diagram.
 Q1, Q2 etc are the temperatures at which the solidification starts and R1,
R2 etc are the temperatures at which solidification completes.
 Although the above figure is drawn for temperature with time as well as
composition at x axis to construct the phase diagram, the actual phase
diagram can be shown for temp with composition which is shown in below
fig 3

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Fig 3. complete phase diagram
Coring miscibility or dendritic segregation:
 Coring or segregation is the non-uniform distribution of constituents in a
metal. Usually a concentration of certain constituents and/or impurities,
arising during freezing and generally persisting throughout subsequent
operations, known as coring.
 As an alloy say Cu-Ni cools through the solidification range, solute Cu is
rejected at the solid-liquid interface. With further cooling, the solute
element is continuously rejected into the liquid phase at solid-liquid
interface and the solid formed remains deficient in copper as compared to
its own parent liquid.
 Since the freezing process is very rapid (ie., non-equilibrium cooling) the
compositional differences arising in freezing persist in the solidified

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 castings. The result of this difference in composition within an individual
grain is known as coring or segregation.

Interpretation of phase diagrams

The rules necessary to interpret the phase diagrams are,
1. the phase that are present
2. the chemical composition of each phase
3. the lever rule (the amount of each phase)

Rule – 1: prediction of phases

 Phase can be predicted only when temp and composition is known, thus a
vertical line drawn (on the phase diagram constructed for bismuth and
antimony and shown in fig. 4) for 30% bismuth and the temp selected as 1200,
900 and 6000F respectively noted as point 1, 2 and 3.
 At point 1 only one phase as liquid and at pt 2 two phases that are liquid and
solid followed by at pt 3 only one phase as solid.
 Similar analysis can be made for any other alloy compositions and temp in the
phase diagram
Rule – 2: Phase composition
 To find out the composition of phases which are stable at a give temp (say
9000F in figure 4 draw a horizontal line (isothermal line), OP at given
temperature.
 Liquid phase (p) has the compositions roughly 62% bismuth and solid phase
(O) has the composition roughly 14% bismuth, of course, the reminder is
antimony in both cases.

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Fig. 4 Interpretation of phase diagram
Rule – 3: Lever arm principle
 To determine the relative amount of two phases, draw a vertical line, AL (in
this case, consider the line drawn at 30%Bi) on the composition scale, which
gives the total or overall composition of the alloy (like 30Bi-70Sb)
 The intersection of this composition vertical line AL on a isothermal line OP is
the fulcrum (noted as point M) of a simple lever system, whereas OM and OP
are two lever arms. The isotherm line OMP is called as a tie line, since it joins
the composition of two phases in equilibrium at a specific temperature.
 The relative lengths of the lever arms multiplied by the amounts of the phase
present must balance, which is called lever rule, since the amount of given
phase multiplied by its lever arm is equal to the amount of the other phase
multiplied by its respective lever arm.

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 The lever rule expressed in mathematical form to determine the relative phases:
MP (62  30)
1. the amount of solid phase =  100   100  66.67%
OP (62  14)
𝑂𝑀 (30−14)
2. the amount of liquid phase = ∗ 100 = (62−14) ∗ 100 = 33.33%
𝑂𝑃

Gibbs phase rule:

 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).
Mathematically, it can be expressed as: P + F = C + 2, where P is the number
of phases (e.g., solid liquid etc), F is the number of degrees of freedom or the
number of physical variables (pressure, temperature and concentration) that
can be independently changed without altering the equilibrium, and C is the
number of components in the system (for instance Cu and Ni are the
components of Cu-Ni phase diagram).
 In metallurgical systems, where pressure is fixed at one atmosphere and the
only variable is temperature, thus actual phase rule is simplified to the
following form;
P + F = C + 1 or
F=C+1–P
Since the degrees of freedom F cannot be less than zero, C+1-P≥0 or P≤C+1,
which means the number of phases (P) in a system cannot exceed the number of
components Plus one.
 Consider, the points X and Y in Fig. 4, to determine the number of degrees of
freedom using the phase rule.
1. Point X, in the region above the liquidus, Number of components, C =
2, since it is a binary system of Bi and Sb, number of phases, P = 1
(liquid), applying the rule, F=C+2-P = 2+2-1 = 3 degrees of freedom
2. Point Y, between the liquidus and solidus, C=2, P = 2, applying rule,
F=C+2-P = 2+2-2 = 2 degrees of freedom.

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 The phase rule becomes particularly useful when dealing with multi-
component systems to determine whether the microstructures are in
equilibrium or not.

Equilibrium cooling and/or heating of solid solution alloy, with its

development of microstructure:
 The very slow cooling, under equilibrium conditions of a particularly 70A-30B
will now be considered to observe the phase change that occur, (refer Fig. 5)

Fig. 5 The slow cooling of &0A-30B alloy with microstructure at various points of
solidification

 This alloy at temp T0 is a homogeneous single-phase liquid solution (fig 5a)

and remained so until temp T1 is reached. Since T1 is on the liquidus line,
freezing or solidification now begins. The first nuclei of solid solution to form,
α1, will be very rich in the higher melting point metal A and will be composed

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 of 95A-5B (rule 1 and 2), just after the start of solidification, the composition
of the liquid is 69A-31B (fig 5b)
 Still lowering the temp up to T2, the liquid composition is at L2 and the solid
solution forming at T2 is α2. Applying rule 1 and 2, α2 is composed of 10B. It
is therefore, as the temp decreases B becomes richer in solid as well in liquid
solution. At T2, crystals of α2, are formed surrounding the α1 composition
cores and also separate dendrites of α2 (fig. 6).

Fig. 6. Schematic view of the alloy 30B at temp T2 before diffusion

 Then at T3, the solid solution will make up approximately three-fourths of all
material present. At this temp (fig. 5 d) the composition of liquid is 42A-58B
and that of solid is 80A-20B. Applying the lever rule (rule 3) at T3, the relative
quantities of α3 and L3 is found to be 73.7% and 26.3% respectively
 Finally, the solidus line, where the temp is noted as T4, the last liquid L4, very
rich in B, solidifies primarily at the grain boundaries (fig 5e). However,
diffusion takes place on further lowering the temp, at T5, all the solid solution
will be of uniform composition α (70A-30B), which is the overall composition
of the alloy (fig 5f)
 The microstructure of a slow-cooled solid solution alloy shown in fig 7,
observed to be only grains and grain boundaries. There is no evidence of any

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 difference in chemical composition inside the grains, exhibits that the diffusion
has made the grain homogenous.

Fig. 7. Microstructure of a solid solution iron alloy at a magnification of 100X

Eutectic system:
 In a eutectic reaction, when a liquid solution of fixed composition, solidifies at
a constant temperature, forms a mixture of two or more solid phases. This
process is reversible, the reaction is expressed as:

 Eutectic system refers to a specific alloy composition, that freezes at a lower

temperature than any other composition (refer Fig. 8.). The eutectic temp and

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 composition determine a point on the phase diagram, where a liquid solidifies
into two different solid simultaneously called as eutectic point.

Fig. 8. Cooling curves for two metals insoluble in solid state

 Figure 8 shows cooling curves for a series of two metals that are insoluble in
the solid state such as Bismuth and Cadmium. The figure also shows, how by
joining a1b1, a2b2,….. points, the equilibrium diagram for a such a system can
be obtained.
 To explain this type of system, it is necessary to consider the cooling and
solidification of three compositions such as 1, 2 and 3 shown in Fig.9.
Point-3: 80%Cd and 20%Bi
 As the temp falls to T1, crystal nuclei of pure Cd begin to form. Since pure Cd
is deposited, it follows that the liquid becomes richer in Bi; on further
decreasing temp to T2, the composition moves on to left 3’ and at T2 more Cd
is deposited and dendrites begin to develop from the already formed nuclei
(fig. 9d).

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Fig. 9. The Bi-Cd equilibrium diagram
 On one hand, the growth of Cd dendrites and the other hand consequent
enrichment of the remaining liquid in Bi, continues until the temp has fallen to
1400C, the eutectic temp in this case. The remaining liquid then contains
40%Cd and 60%Bi, the eutectic composition.
Point-1: 20%Cd and 80%Bi
 Contrary to point 3, in this case crystal of pure Bi form first, enriching the melt
with Cd. The composition of the melt or liquid moves to right until ultimately
the point E is reached and the remaining liquid solidifies as eutectic.
Point-2: 40%Cd and 60%Bi
 No solidification occurs until the melt reaches the eutectic temp, 1400C, the
two pure metals crystallize together to give a characteristically fine aggregate
known as eutectic (fig 9c)

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Congruent melting intermediate phase:
 When one phase changes into another phase isothermally (ie., at constant
temp) and without any change in chemical composition, it is said to be
congruent phase change or congruent transformation.
 Any intermediate phase may be treated as another component on a phase
diagram. If this phase has a narrow range of composition, it is then represented
on the diagram as a vertical line and labeled with a chemical formula of the
compound (refer fig 10) which is indicated as AmBn, where m and n are the
number of atoms combined in the compound.

Fig. 10. Composition and melting point of pure A, pure B and a compound AmBn
 For example, magnesium and tin form an intermediate phase which has the
chemical formula Mg2Sn. In this case, Mg is equivalent to A; 2 is equivalent
to m; Sn, is equivalent to B and n is equal to 1.

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Peritectic Reaction:
 In the Peritectic reaction a liquid and solid react isothermally to form a new
solid on cooling, the reaction expressed in general as;

Transformations in the solid state:

Allotropy
 Several metals may exist in more than one type of crystal structure depending
upon the temperature. Iron, tin manganese and cobalt are the examples of
metals which exhibit this property known as allotropy.
 Fig. 11a,b shows a cooling curve for pure iron with allotropic forms of iron
marked over it. Iron is molten above 15390C. it solidifies in the B.C.C δ
(delta)
 On further cooling at 14000C, a phase change occurs and the atoms rearrange
themselves into the γ (gamma) form which is FCC and non-magnetic. On still
further cooling at 9100C, another phase change occurs from FCC non-magnetic
γ-iron to BCC non-magnetic α (alpha) iron.
 Finally at 7680C, the α-iron (BCC) becomes magnetic without a change in
lattice structure.

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 Fig. 11a Allotropic forms of iron

Figure 11b. Cooling curve for pure iron showing allotropic behaviour of iron

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Eutectoid Reaction:
 A solid phase transforms on cooling into two new solid phases, the general
equation can be written as:

Peritectoid reaction:
 The two different solid phase on cooling transforms into a new solid phase, the
equation as follows:

 This new solid phase is usually an intermediate alloy, but it may also be a solid
solution.

Study of important binary phase diagram and the relation between PD

and properties:
Iron carbon equilibrium diagram:

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 2.11%

0.77%

Important Features:
Phases Present
L - liquid

-iron -iron -iron (Ferrite) Fe3C (Cementite)

Bcc structure (Austenite) Bcc structure Orthorhombic
Paramagnetic Fcc structure Fairly ductile Hard, Brittle
Ductile Ferromagnetic 
Non-magnetic

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2. Invariant Reactions

Max. solubility of C in ferrite=0.022%; Max. solubility of C in austenite =2.11%

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Crystal Structure and Microstructure of Phases
 -iron (Ferrite)

a-iron (B.C.C) unit cell. Microstructure of ferrite.

 -iron (Austenite)

Face-centred cubic crystal unit cell. Microstructure of austenite.

Properties of Steel Constituents

Austenite Ferrite Cementite Pearlite

Structure FCC BCC Orthorhombic Alternating
layers of
ferrite and
cementite
Strength Weak Weak Strong Between
ferrite and
cementite
Ductility Very ductile Very Low ductility, Between
ductile brittle ferrite and
cementite
Carbon up to 2.11 low, up to Fe:C = 3:1 Fixed carbon
Solubility wt.% C 0.0218 content
wt.% C

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