4 PHASE DIAGRAMS

Introduction
In a material’s system, matter can exist in three states namely:- gas, liquid and solid. Matter
can achieve a state of equilibrium where two or all of the above states exist simultaneously.
Equilibrium can exist not only between the liquid and vapor phase of a substance but also
between the solid and liquid phases, and the solid and gas phases of a substance.

Definitions:
System - Any portion of the universe which is of interest and can be studied experimentally.

Phase- any particular portion of a system, which is physically homogeneous in state , crystal
structure, has a specific composition, and can be mechanically removed or separated from
any other phase in the system.

Thus a mixture of ice and water constitutes two phases, so does a mixture of water and ether.
But a dilute solution of salt in water is a single phase. Matter with more than one phase is
called a mixture and has a phase boundary.

Phase Diagram
A phase diagram is a graphical way to depict the effects of pressure, temperature and
composition on the phase of a substance. They provide a graphical means of presenting the
results of experimental studies of complex natural processes, such that at a given temperature
and pressure for a specific system at equilibrium the phase or phases present can be
determined.

Equilibrium - The condition of minimum energy for the system such that the state of a
reaction will not change with time provided that pressure and temperature are kept constant.

Three practical criteria could be used to test for equilibrium.

1. Time - with time the system does not change its physical or chemical makeup.
2. Approach equilibrium from two directions,
3. Attainment of equilibrium by using different reactants and procedures.

Component - the smallest number of independent variable chemical constituents necessary to

define any phase in the system.
• components may be oxides, elements or minerals, dependant on the system being
examined.
For example, experiments carried out in the H2O system, show that the phases which appear
over a wide temperature and pressure range are ice, liquid water and water vapour. The
composition of each phase is H2O and only one chemical parameter or component is required
to describe the composition of each phase.

In materials science, gas phases are of no real relevance, and much emphasis is placed on
liquid and solid phases.

Many solid phases exist, the difference between them being the nature of their atomic
arrangement, or crystal structure. A phase can exist over a range of temperatures and
compositions, but it's atomic structure will remain the same. There may be only one gas and
one liquid phase for an alloy at a given temperature and composition, but there can be many
solid phases.

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UNARY SYSTEMS
Systems which can be defined by a single component.
Examples include:-
H2O system
SiO2 system

H2O system:
In this system, phase has same composition i.e H2O.
Pressure

The curves indicate the conditions of temperature and pressure under which equilibrium
between different phases of a substance can exist

• The vapor pressure curve is the border between the liquid and gaseous states of the
substance
• For a given temperature, it tells us the vapor pressure of the substance
• The vapor pressure curve ends at the critical point.
The critical point is the temperature above which the gas cannot be liquefied no matter how
much pressure is applied (the kinetic energy simply is too great for attractive forces to
overcome, regardless of the applied pressure)
• The line between the gas and solid phase indicates the vapor pressure of the solid as it
sublimes at different temperatures
• The line between the solid and liquid phases indicates the melting temperature of the
solid as a function of pressure
• For most substances the solid is denser than the liquid
• An increase in pressure usually favors the more dense solid phase
• Usually higher temperatures are required to melt the solid phase at higher
pressures
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 • The "triple point" is the particular condition of temperature and pressure where all
three physical states are in equilibrium
• Regions not on a line represent conditions of temperature and pressure where only
one particular phase is present
• Gases are most likely under conditions of high temperature
• Solids are most likely under conditions of high pressure

• The frozen state of water (ice) is actually less dense than the liquid state, thus, the
liquid state is more compact than the solid state
• Increasing pressure, which will favor compactness of the molecules, will thus
favor the liquid state
Increasing pressure will thus lower the temperature at which the solid will melt
• The melting curve slopes to the left, unlike most compounds
• At 100 °C the vapor pressure of water is 760 torr or 1 atm, thus at this temperature
water will boil if it is at 1 atm of pressure
• At pressures below 4.58 torr, water will be present as either a gas or solid, there can
be no liquid phase

The phase rule

For a system at equilibrium the phase rule relates:
• P = number of phases that can coexist, to
• C = number of components making up the phases, and
• F = degrees of freedom.
• Where these three variables are related in the equation
P+F=C+2
The degrees of freedom represent the environmental conditions which can be independently
varied without changing the number of phases in the system. Conditions include:
• Temperature,
• Pressure,
• Chemical Composition,
• pH,
• Eh,
• Oxygen Fugacity.

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 Simplified H2O system
Applying the phase rule to the simplified H2O system above,
Phase rule becomes P + F = 3, because we are dealing with a one component system (C = 1).
4. At A
• P = 1 - water
• F = 2 - two degrees of freedom,
• So to maintain equilibrium, i.e. have one phase (water) stable temperature and
pressure may vary independently.
5. At B
Point B lies on the boundary curve separating Ice from steam field,
• P = 2 - Ice and Steam,
• F = 1 - one degree of freedom,
• To maintain equilibrium, i.e., to keep the 2 phases stable, one must choose an
arbitrary value for pressure or temperature, which will automatically fix either
temperature or pressure.
6. At T
• P = 3 - Water, Ice, Steam
• F = 0 - No degrees of freedom,
• All three phases coexist at equilibrium. Can not change pressure or
temperature without causing the system to move away from Point T, which
will cause one or more of the stable phases to disappear.
Therefore the maximum number of phase which can (with stability ) coexist in a one
component system is three, and they do so only if there are no degrees of freedom.

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 Al2SiO5 system

For the Al2SiO5 system, at a point in the field of kyanite stability, kyanite is the only phase
present, P=1. F is 2 at this point, (i.e one could change both temperature and pressure by
small amounts without affecting the number of phases present). The area of kyanite stability
on the phase diagram is a di-variant field (variance or degrees of freedom, F =2).
At a point on the phase boundary between kyanite and sillimanite, the number of phases P =
2. Using the phase rule, F = 1 (i.e there is one degree of freedom – one independent variable).
A change in pressure, results precipitates a corresponding change in temperature (in order to
keep both phases stable). The phase assemblage is said to be univariant in this case, and the
phase boundaries are univarient lines (or curves in the more general case.

At the point where all three univariant lines intersect, 3 phases:- kyanite, andalusite, and
sillimanite all coexist at equilibrium. This is the only point where all three phases can coexist.
For this case, P=3, and F, from the phase rule, is 0. There are no degrees of freedom, (i.e any
change in pressure or temperature will result in a change in the number of phases). The
three-phase assemblage in a one component system is said to be invariant.

BINARY SYSTEMS
On a two component or binary diagram, three variables can be represented. These are
generally pressure (P), temperature (T) and compositional changes (X) on a two dimensional
diagram.
To graphically represent a Binary diagram one variable must be kept constant, which is
usually P, and the phase diagram is plotted as a T-X diagram for a specific Pressure.

Alloying systems
Material properties (except electrical conductivity, and to some extent the ductility and
corrosion resistance) are not at their best in the pure metal. The other properties (strength,
hardness, toughness, wear resistance, etc.,) are improved by alloying. We define an alloy as a
combination of two or more elements (the major component being a metal) into a single
material.

Alloys are formed by melting the alloying elements together. In the liquid state, nearly all
metals are miscible in all proportions. The liquid mixture is then cooled and on solidification
any of the following may happen:
i) the metals may be completely soluble in the solid state.
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 ii) they may be completely insoluble in solid state.
iii) they may be partially soluble in the solid state.
iv) an inter-metallic compound may form between the metals.

Solid Solutions
Solid state solutions may form either by substitution or as interstitial solutions. In
substitutional solid solutions, atoms of the solute substitute those of the solvent in the latter's
crystal lattice. The substitution may be ordered or random. For substitutional solid solution
to take place, the atoms of the two elements must be approximately equal in size and have
comparable electronic structure. Examples: Zn/Cu (brass), Au/Ag, Cu/Ni.

In interstitial solutions, a comparatively small atom takes the interstice between the atoms of
the solvent. The bonds in solid solutions are predominantly metallic and the crystal structure
remains the same as that of the solvent. Solid solutions are generally soft and ductile.

Inter-metallic Compounds
Metals form compounds between themselves or with non-metals which are termed
intermetallic compounds. The compounds are hard and brittle with well defined melting
points (solid solutions melt over a range of temperatures). Their crystal structures are
complex (with each unit cell having up to 40 atoms or more). The bonds may be ionic,
covalent or metallic. The 3 types of inter-metallic compounds are:

i) Valency intermetallic compounds: these form between electropositive metals and

fairly electronegative metals in groups IV(b), V(b) and VI(b) of the periodic table. Here, the
usual rules of valency are followed as in normal compounds and the bonds are either ionic or
covalent. Examples: Mg3Sb2, Mg2Sn, Mg3Bi2.

ii) Electron intermetallic compounds: these form between metals of comparable

electrochemical properties with atoms whose sizes are approximately equal. The rules of
valency are not followed but a fixed ratio is maintained. They are usually non-stoichiometric
i.e., the same two metals can form several compounds with different proportions. The
bonding is essentially metallic. Examples: CuZn, Cu3Al, Cu5Sn, Cu5Zn8, Cu9Al4, Ag5Zn8.

iii) Interstitial compounds: form between metals and non-metals. The small non-metal
atoms take the interstice between the metal atoms and are bonded to them (metal atoms) by
mixed ionic, covalent and metallic bonds. Examples: Fe3C, WC, iron nitrites.

Binary Phase Diagrams.

Useful engineering alloys are built from solid solutions and inter-metallic compounds. In
doing this, use is made of equilibrium or phase diagrams which are charts showing the
relationships between composition, temperature and structure in an alloy system. They are
constituted 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.

The x--axis of the phase diagram represents the composition -- from 100% metal A to 100%
metal B. The y-axis represents the temperature.

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Types of Binary Phase Diagrams
(A) Complete Solubility in Solid State
Pure metal A will solidify at MP(A) and pure metal B at MP(B) (see fig. below). If the melt
contains some B, this will raise the solidification temperature of A. The effect increases with
increase in the quantity (ratio) of B until we reach MP(B) (assume MP(B) is higher than
MP(A)).

MPB

Liquidus

Solidus

MPA

%A 100 %A 0
%B 0 Composition
Complete solubility in the solid state %B 100
Further, solidification of mixtures does not take place at a distinct temperature but over a
temperature range. We can therefore mark the temperature at which solidification starts and
the temperature at which it ends for each composition. The line joining all those points at
which solidification starts is termed the liquidus.
Above the liquidus, only liquid exists. The line joining the temperatures at which
solidification ends is termed the solidus. Below the solidus, we have only solid (the solid
solution). In between the solidus and the liquidus, solidification is incomplete hence we have
a mixture of solid and liquid.

This type of reaction can only occur where solid solution is by substitution. Common
examples are Cu--Ni; Au--Ag; while less common examples are Bi--Sb; Ag--Pd.

Another good example of a complete solid solution is displayed in the plagioclase feldspars.
In this case the solid solution is between the end members albite (NaAlSi3O8) and anorthite
(CaAl2Si2O8). In order to maintain charge balance we cannot simply substitute Na+ for Ca+2,
so this solid solution is what is called a coupled solid solution. In this case Na+Si+4 is
substituted for Ca+2Al+3 in the plagioclase structure to produce intermediate compositions of
plagioclase.

Because the elements that substitute are not exactly the same size (they are similar in size)
the amount of substitution is dependent on temperature and pressure and the solid solutions
behave in a somewhat orderly fashion as illustrated below.

Since plagioclase is one of the most common minerals in the earth's crust, we will discuss the
phase diagram for the plagioclase system.

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 Plagioclase system

The phase relations in the plagioclase system are shown in the Figure above at constant
pressure equal to that of the atmosphere (atmospheric pressure is 1 bar). At temperatures
above the liquidus everything is liquid, below the solidus everything is solid (crystals of
plagioclase solid solution). At temperatures between the solidus and liquidus crystals of
plagioclase solid solution coexist in equilibrium with liquid.

Pure albite melts (or crystallizes) at 1118oC, and pure anorthite melts (or crystallizes) at
1500oC. Any composition of plagioclase between the two end members melts or crystallizes
over a range of temperatures unlike the pure end members which have only one melting point.
Thus from the diagram, a solid solution containing 50% albite and 50% anorthite
(Ab50An50) begins to melt at 1220o, (i.e point F), and the melting is complete at 1410o,
(point A). Inversely, if a melt of composition Ab50An50 is cooled it will begin to crystallize
at 1410o and will be completely crystalline at 1220o.

Conditions for complete (unlimited) solubility

In order for an alloy system, such as copper-nickel, to have unlimited solid solubility, certain
conditions must be satisfied. These conditions, the Hume-Rothery rules, are as follows:
1. Size factor: The atoms must be of similar size, with no more than a 15 % difference in
atomic radius, in order to minimise the lattice strain.
2. Crystal structure: The materials must have the same crystal structure; otherwise, there is
some point at which a transition occurs from one phase to a second phase with a different
structure.
3. Valence: The atoms must have the same valence; otherwise, the valence electron
difference encourages the formation of compounds rather than solutions.
4. Electronegativity: The atoms must have approximately the same electronegativity. If the
electronegativities differ significantly, compounds again form - as when sodium and chlorine
combine to form sodium chloride.
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Hume-Rothery's conditions must be met, but they are not necessarily sufficient, for two
metals to have unlimited solid solubility.

Similar behaviour is observed between certain compounds, including ceramic materials. The
figure below shows schematically the structure of MgO and NiO. But the Mg and Ni ions are
similar in size and valence and, consequently, can replace one another in a sodium chloride
type of lattice, forming a complete series of solid solutions of the form (Mg, Ni)O.

The solubility of interstitial atoms is always limited. Interstitial atoms are much smaller than
the atoms of the host element, thereby violating the first Hume-Rothery’s conditions

(B) Complete Insolubility in Solid State

Here, the presence of B in A lowers the solidification point of A in a similar manner to the
lowering of solidification point of water if it has dissolved salts. Similarly, presence of A in
B lowers its (B's) solidification point. When the two sets of points are joined, the liquidii
meet at point E (see fig. below). On cooling a liquid whose composition is to the left of point
E, solidification of A will start at the liquidus. The liquid which is left will be richer in B.
This will continue until the liquid left has the composition CE. The same happens with
compositions to the right of E - this time with precipitation of B. At point E, precipitation of
both A and B is possible and proceeds as follows:
i) at some local point, A precipitates
ii) the surrounding liquid becomes richer in B moving the conditions to the right of E
iii) B precipitates in the area surrounding the original precipitate of A and conditions shift
to the left of E
iv) A precipitates and the process is repeated.

CE

Complete insolubility in solid state

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Thus the resulting precipitate consists of alternate layers of A and B - constituting a
EUTECTIC. The point E is therefore called the eutectic point. It is the lowest temperature at
which the mixture can stay wholly liquid and is important for casting operations. The
corresponding composition CE and the corresponding temperature TE are termed eutectic
composition and eutectic temperature respectively. Since for every composition
solidification is complete at point E, the solidus is an isothermal (a constant temperature line)
through E.

The reaction at the eutectic point, i.e., the simultaneous precipitation of two solids from a
liquid at the eutectic, point, can be written:

cooling
L S1 + S 2
heating

and is termed the eutectic reaction.

Cases of complete insolubility in metals are rare. Examples are calcium/bismuth;

silver/silicon; and gold/silicon.

(C) Partial Solubility in Solid State

This case is similar to that of complete insolubility -- but when A (say) solidifies, it does so
with some B dissolved in it. Thus the solid precipitating is α (a solution of B in A).
Similarly, instead of B precipitating, β = a solution of A in B, solidifies. In general (though
not always), the solubilities are a maximum at the eutectic temperature. Thus the equilibrium
diagram is as shown in fig. below.

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 MP(A)
L
MP(B)

L+β
TEMP.

α E
β

α+
β

A B
Partial solubility in the solid state

This type of equilibrium diagram is the most common in metals and examples are Ag/Cu;
Al/Si; Pb/Sn; Pb/Sb; Bi/Sn; Cd/Pb.

(D) Systems with Intermetallic Compound

Let the intermetallic compound be AxBy. The equilibrium diagram can then be divided into
two parts: one between A and AxBy and the other between AxBy and B.

MP(A)
L L
MP(B)
L+
L+
L+ AxBy
AxBy
TEMP.

L+
α E2 β β
E1

α+ β + AxBy

A AxBy B
System having an inter-metallic compound

In theory, each of the two parts can be any of the shapes already considered (complete
solubility, complete insolubility or partial solubility). In most cases however, neither metal is
soluble in the intermetallic compound while there is still some partial solubility of the metals
in each other. The most general form of the equilibrium diagram is therefore as shown in fig.
above.

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The position of AxBy on the equilibrium diagram can be easily found from the atomic
weights:
[Link]. By
Wt. % B =
at. wt. By + at. wt. Ax
Usually, only one portion of the diagram is of technological importance. Examples Pb/Mg;
Cu/Al; Fe/C; Mg/Sn.

(E) Systems with Eutectoid Reaction

In alloying systems where one of the components has a temperature based polymorphism, a
change in solubility occurs when the polymorph changes. The excess solute must then
precipitate a new phase -- thus we will have two solids precipitating from one solid, at the
change of polymorph. Like the eutectic reaction, the two solids precipitate simultaneously
and form alternate layers.

γ + L L
γ

Eutectic
Eutectoid
γ + Led
723 oC
Pe

α + Per

Le
Per + C

100% FE %C

Eutectoid reaction
This reaction is termed the eutectoid (eutectic like) reaction and may be written:

cooling
S1 S 2 + S3
heating

The best examples are the decomposition of austenite in the Fe--C system and the formation
of α and γ2 from β in the Cu--Al system. Both will be studied further later.

(F) Systems with Peritectic Reaction

In some systems, a solid already precipitated reacts with excess liquid to form a new solid.
This reaction is termed peritectic reaction and may be written:

cooling
S1 + L S2
heating

The equilibrium diagram then has the shape shown in fig. below and can be seen to be the
inverse of the eutectic reaction (a mirror image of the diagram along PR gives the eutectic
reaction).

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 X1 X2

MP(A) L
T1

L + S1
S1 T2
P Q R
TP

S2 + L

S 1 + S2 MP(B)
S2

A CP B
% COM

System showing the peritectic reaction

The peritectic reaction can only take place if S1 and liquid are both present together at the
peritectic temperature Tp for compositions between P and R. Taking alloy X1, precipitation
of S1 will start at T1 and continue until liquid left has composition R. Here, the peritectic
reaction takes place to produce S2 of composition Q. Since there is more S1 than liquid, the
liquid is used up leaving some S1. Hence below Tp, we have a mixture of S1 and S2. For
alloy of composition X2, S1 will again be deposited until Tp. When the peritectic reaction
takes place, S1 is used up first. Thus below Tp, we have S2 and liquid. The remaining
liquid then forms S2 in the normal manner.

COMPOSITION AND QUANTITIES OF PHASES

In two phase areas, the composition and quantities of the phases are determined as follows:

(i) for the chemical composition, an isothermal is drawn through the temperature of interest.
The intersection of the isothermal with the phase boundaries gives the compositions. For
example the alloy shown in fig. below, the composition of solid at T1 is CP while the
composition of liquid is CQ.

(ii) for quantities (or ratios) of the phases, the lever rule is applicable. It states: let the
intersection of the isothermal and the line representing the composition (F in fig. below) be
the fulcrum of a horizontal lever; -- the lengths of the lever arms to the phase boundaries
times the ratios must balance. Thus if RS = ratio of solid and RL = ratio of liquid,

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 MPB

Liquidus

P F Q
T1

Solidus

MPA

%A 100 CP CQ %A 0
Composition
%B 0 %B 100

PF x RS = FQ x RL But RL = 1 - RS

⇒ PF x RS = FQ(1-RS) RS (PF+FQ) = FQ

or RS = FQ / PQ (since PF + FQ = PQ)

Similarly RL = PF / PQ

These can be easily remembered as "opposite"/"total".

Additional Notes:

1. DENDRITES
Solidification from the melt occurs by nucleation and growth. Tiny nuclei form at various
parts of the melt and then grow at the expense of the liquid surrounding them. The growth
may be more rapid along certain crystallographic directions resulting in branched crystals
called dendrites. When dendrites of different orientation touch, growth stops. The rest of the
melt then solidifies and the contact surfaces become the grain boundaries.

2. CORING.
The precipitating solid has a different composition as the temperature decreases. For example,
in fig. above. the first solid to precipitate will have a higher proportion of B than the last. The
resulting grain or crystal will thus have varying composition from the centre (more B) to the
edges (less B) and is said to be cored. Coring can only be avoided (or reduced) if the cooling
rate is extremely low to allow diffusion to take place. Cored casting have inferior mechanical
properties compared to homogeneous ones and hence cored casting are sometimes re--heated
to just below the solidus temperature and kept at this temperature to allow diffusion to take
place. This procedure is termed homogenization.

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