Phase Diagrams

Mixtures –Solutions –Phases

• Almost all materials have more than one phase in them.
Thus engineering materials attain their special
properties.
• Macroscopic basic unit of a material is called
component. It refers to a independent chemical species.
The components of a system may be elements, ions or
compounds.
• A phase can be defined as a homogeneous portion of a
system that has uniform physical and chemical
characteristics i.e. it is a physically distinct from other
phases, chemically homogeneous and mechanically
separable portion of a system.
• A component can exist in many phases.
E.g.: Water exists as ice, liquid water, and water vapour.
Carbon exists as graphite and diamond.
• 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.
• A solution(liquid or solid) is phase with more
than one component; a mixture is a material with
more than one phase.
• Solute (minor component of two in a solution)
does not change the structural pattern of the
solvent, and the composition of any solution can
be varied.
• In mixtures, there are different phases, each with
its own atomic arrangement. It is possible to
have a mixture of two different solutions!
 Gibbs phase rule
• In a system under a set of conditions, number of phases
(P) exist can be related to the number of components (C)
and degrees of freedom (F) by Gibbs phase rule.
• Degrees of freedom refers to the number of independent
variables (e.g.: pressure, temperature) that can be varied
individually to effect changes in a system.
• Thermodynamically derived Gibbs phase rule:
• In practical conditions for metallurgical and materials
systems, pressure can be treated as a constant (1atm.).
Thus Condensed Gibbs phase rule is written as:
Equilibrium phase diagram
• A diagram that depicts existence of different phases of a
system under equilibrium is termed as phase diagram.
• It is actually a collection of solubility limit curves. It is also
known as equilibrium or constitutional diagram.
• Equilibrium phase diagrams represent the relationships
between temperature, compositions and the quantities of
phases at equilibrium.
• These diagrams do not indicate the dynamics when one
phase transforms into another.
• Useful terminology related to phase diagrams: liquidus,
solidus, solvus, terminal solid solution, invariant reaction,
intermediate solid solution, inter-metallic compound, etc.
• Phase diagrams are classified according to the number
of component present in a particular system.
Phase diagram –Useful information

• Important information, useful in materials development

and selection, obtainable from a phase diagram.
• It shows phases present at different compositions and
temperatures under slow cooling (equilibrium)conditions.
• It indicates equilibrium solid solubility of one element/
compound in another.
• It suggests temperature at which an alloy starts to
solidify and the range of solidification.
• It signals the temperature at which different phases start
to melt.
• Amount of each phase in a two-phase mixture can be
obtained.
Unary phase diagram
• If a system consists of just one component (e.g. water),
equilibrium of phases exist is depicted by unary phase
diagram. The component may exist in different forms,
thus variables here are –temperature and pressure.
Binary phase diagram
• If a system consists of two components, equilibrium of
phases exist is depicted by binary phase diagram. For
most systems, pressure is constant, thus independently
variable parameters are –temperature and composition.
• Two components can be either two metals (Cu and Ni),
or a metal and a compound (Fe and Fe3C), or two
compounds (Al2O3 and Si2O3), etc.
• Two component systems are classified based on extent
of mutual solid solubility –(a) completely soluble in both
liquid and solid phases (isomorphous system) and (b)
completely soluble in liquid phase whereas solubility is
limited in solid state (Eutectic system).
• For isomorphous system -E.g.:Cu-Ni, Ag-Au, Ge-Si,
Al2O3-Cr2O3.
Hume-Ruthery conditions
• Extent of solid solubility in a two element system can be
predicted based on Hume-Ruthery conditions.
• If the system obeys these conditions, then complete
solid solubility can be expected.
• Hume-Ruthery conditions:
• -Crystal structure of each element of solid solution must
be the same.
• -Size of atoms of each two elements must not differ by
more than 15%.
• -Elements should not form compounds with each other
i.e. there should be no appreciable difference in the
electro-negativities of the two elements.
• -Elements should have the same valence.
 Isomorphous binary system
• An isomorphous system –phase diagram and corresponding
microstructural changes.
Tie line –Lever rule
• At a point in a phase diagram, phases present and their
composition (tie-line method) along with relative fraction
of phases (lever rule) can be computed.

• Procedure to find equilibrium concentrations of phases.

-A tie-line or isotherm(UV) is drawn across two-phase

region to intersect the boundaries of the region.
-Perpendiculars are dropped from these intersections to the
composition axis, represented by U’ and V’, from which
each of each phase is read. U’ represents composition of
liquid phase and V’ represents composition of solid
phase as intersection U meets liquidus line and V meets
solidus line.
 Procedure to find equilibrium relative amounts of
phases (lever rule):
• -A tie-line is constructed across the two phase region at
the temperature of the alloy to intersect the region
boundaries.
• -The relative amount of a phase is computed by taking
the length of tie line from overall composition to the
phase boundary for the other phase, and dividing by the
total tie-line length. In previous figure, relative amount of
liquid and solid phases is given respectively by:
 Eutectic binary system
• Many of the binary systems with limited solubility are of
eutectic type –eutectic alloy of eutectic composition
solidifies at the end of solidification at eutectic temperature.
• E.g.: Cu-Ag,
Pb-Sn
Eutectic system –Cooling curve –Microstructure
Eutectic system –Cooling curve –Microstructure
Eutectic system –Cooling curve –Microstructure
Invariant reactions
• Observed triple point in unary phase diagram for
water?
• How about eutectic point in binary phase diagram?
• These points are specific in the sense that they occur
only at that particular conditions of concentration,
temperature, pressure etc.
• Try changing any of the variable, it does not exist i.e.
phases are not equilibrium any more!
• Hence they are known as invariant points, and
represents invariant reactions.
• In binary systems, we will come across many number of
invariant reactions!
Intermediate phases
• Invariant reactions result in different product phases –
terminal phases and intermediate phases.
• Intermediate phases are either of varying composition
(intermediate solid solution) or fixed composition (inter-
metallic compound).
• Occurrence of intermediate phases cannot be readily
predicted from the nature of the pure components!
• Inter-metallic compounds differ from other chemical
compounds in that the bonding is primarily metallic
rather than ionic or covalent.
• E.g.:Fe3C is metallic, where as MgO is covalent.
• When using the lever rules, inter-metallic compounds are
treated like any other phase.
 Congruent, Incongruent transformations
• Phase transformations are two kinds –congruent and
incongruent.
• Congruent transformation involves no compositional changes. It
usually occurs at a temperature.
• E.g.: Allotropic transformations, melting of pure a substance.
• During incongruent transformations, at least one phase will
undergo compositional change. E.g.:All invariant reactions,
melting of isomorphous alloy.
• Intermediate phases are sometimes classified on the basis of
whether they melt congruently or incongruently.
• E.g.:MgNi2, for example, melts congruently whereas Mg2Ni melts
incongruently since it undergoes peritectic decomposition.
Fe-C binary system –Phase transformations