LECTURE 7

HMATE 315
INTRODUCTION TO PHASE DIAGRAMS

• Definitions and basic concepts

• Phases and microstructure
• Binary isomorphous systems (complete solid solubility)
• Binary eutectic systems (limited solid solubility)
• Eutectic and eutectoid alloys.
• Binary systems with intermediate phases/compounds
• The iron-carbon system (steel and cast iron)
WHAT IS A PHASE?

• Phase – a portion of a system that has uniform physical and chemical characteristics. Two
distinct phases in a system have distinct physical and/or chemical characteristics (e.g.
water and ice, water and oil) and are separated from each other by definite phase
boundaries. A phase may contain one or more components and may be defined using the
following characteristics
i. The same structure or atomic arrangement throughout;
ii. Roughly the same composition and properties throughout; and
iii. A definite interface between the phase and any surrounding or adjoining phases.
 MICROSTRUCTURE

• The properties of an alloy depend not only on proportions of the phases but also on how
they are arranged structurally at the microscopic level. Thus, the microstructure is
specified by the number of phases, their proportions, and their arrangement in space.
Fe-Fe3C matrix   Flakes of Graphite
Microstructure of cast Iron
• The long gray regions are flakes of graphite.

• The matrix is a fine mixture of BCC Fe and Fe3C compound.

• At room temperature and pressure Fe has a BCC structure but as temperature increases,
allotropic transformation occurs and it transforms to austenite that has an FCC crystal
structure at T
• NB Phase diagrams will help us to understand and predict microstructures.
PHASE DIAGRAMS

• Phase diagram is a representation that is usually in the form of a graph of all the
equilibrium phases as a function of temperature, pressure, and composition.
• For one component systems, the equilibrium state of the system is defined by two
independent parameters (P and T), (T and V), or (P and V).
PHASE DIAGRAM OF WATER
PHASE DIAGRAMS FOR BINARY SYSTEMS

• A phase diagrams show what phases exist at equilibrium and what phase transformations we
can expect when we change one of the parameters of the system.
• Real materials are almost always mixtures of different elements rather than pure substances:
in addition to T and P, composition are also variables
• In most cases pressure is assumed to be constant.
• Phase diagrams for materials with more than two components are complex and difficult to
represent. These systems are usually called, ternary systems.
• .
Figure below shows the Cr-Ni-Fe ternary phase diagram
 BINARY ISOMORPHOUS SYSTEMS (I)

• Shows complete solubility of the two components (both in the liquid and solid phases.

 
EXAMPLE II

• Isomorphous system: Cu-Ni (the complete solubility occurs because both Cu and Ni
have the same crystal structure, FCC, similar radii and electronegativity).
EXAMPLE III

• In one-component system melting occurs at a well-defined melting temperature. In a

binary system melting occurs over the range of temperatures, between the solidus and
liquidus lines. Solid and liquid phases are at equilibrium with each other in this
temperature range.
Isopleth line
• For a given temperature and composition we can use a phase diagram to determine:
i. The phases that are present
ii. Compositions of the phases.
• FINDING THE COMPOSITION IN A TWO-PHASE REGION:
i. Locate composition and temperature in diagram
ii. In a two phase regions draw the tie line or isotherm
iii. Note the intersection with phase boundaries. Read compositions at the intersections.
iv. The liquid and solid phases have these compositions.
DETERMINING THE PHASE AMOUNTS.

• By making use of a tie line and the Lever rule, you can determine the phase amounts in
any phase diagram.
i. Locate composition and temperature in diagram
ii. In two phase regions draw the tie line or isotherm
iii. Fraction of a phase is determined by taking the length of the tie line to the phase
boundary for the other phase, and dividing by the total length of tie line
DETERMINE THE PHASE COMPOSITIONS AND
AMOUNTS AT POINT B.
• =1
DEVELOPMENT OF MICROSTRUCTURE IN
ISOMORPHOUS ALLOYS.
• Solidification in the solid + liquid phase occurs gradually upon cooling from the liquidus
line.
• The composition of the solid and the liquid change gradually during cooling (as can be
determined by the tie-line method.)
• Nuclei of the solid phase form and they grow to consume all the liquid at the solidus line.
BINARY EUTECTIC SYSTEMS
systems (alloys) with limited solubility

• Three single phase regions ( - solid solution of Ag in Cu matrix, = solid solution of Cu in

Ag matrix, L - liquid)
EUTECTIC ALLOYS

• The alloy is produced as a result of a eutectic reaction.

• A eutectic alloy has the lowest melting point for the alloy system.
• Also has the highest tensile strength.
• A eutectic mixture solidifies without change in temperature.
PHASE AMOUNT AND COMPOSITION OF EUTECTIC ALLOYS

• phase amounts and composition are constant for the eutectic alloy at the eutectic
temperature
• to determine the phase amount and composition of the eutectic alloy, consider the straight
line at the eutectic temperature as a tie line
EXAMPLE II

• Eutectic or invariant point - Liquid

• and two solid phases co-exist in equilibrium at the eutectic composition CE and the
eutectic temperature TE

• Eutectic isotherm - the horizontal solidus line at TE.

 
Determine the amounts of α and β in the eutectic alloy at the eutectic temperature
Write the eutectic reaction.
MICROSTRUCTURE OF EUTECTIC ALLOYS

• eutectic alloys have lamellar structure.

• the two solid phases form a layered microstructure.
• Distance between the centre of the layer of a phase to the centre of the consecutive layer
of the same phase is called lamellar spacing
• Rate of cooling has a significant effect on lamellar spacing
• Rapid cooling suppresses diffusion processes and results in fine lamellar structure.
MECHANICAL PROPERTIES OF EUTECTIC ALLOYS.

• eutectic alloys have the highest strength possible for the alloy system.
HYPOEUTECTIC AND HYPER-EUTECTIC ALLOYS

• Hypoeutectic alloys have chemical composition less than that of the eutectic alloy.
• Hypereutectic alloys have chemical composition higher than that of the eutectic alloy.
• At temperatures higher than the liquidus, the alloy is completely liquid
• Below liquidus, liquid begins to solidify as α [this is called pro-eutectic α]
• At eutectic temperature, liquid solidifies as per the eutectic reaction to form two solid [the
lamellar structure grows on the pro-eutectic α]
• Rest of liquid will solidify into the eutectic mixture of α and β
EUTECTOID ALLOYS

• The alloy is produced as a result of a eutectoid reaction

• eutectoid reactions are solid state reactions and occur on already existing solids [called
prior grains]
DETERMINATION OF PHASE COMPOSITION AND PHASE
AMOUNT OF THE EUTECTOID ALLOY IS THE SAME AS WITH
THE EUTECTIC ALLOY.
MICROSTRUCTURE OF EUTECTOID ALLOYS

• Eutectoid alloys also have lamellar structure.

• lamellar spacing depends on:
i. Size of prior grains- the finer the prior grains the smaller the. Lamellar spacing [how
would you ensure prior grans are fine?]
ii. Rate of cooling of the eutectoid mixture.
HYPO- AND HYPER- EUTECTOID ALLOYS

• Hypo eutectoid alloys have chemical composition less than that of the eutectoid alloy.
• Hypereutectoid alloys have chemical composition higher than that of the eutectoid alloy
i. initial solid contains 100% γ phase- this is a solid solution
ii. as temperature decreases, α phase is precipitated at the grain boundaries of γ [grain
boundaries are high energy regions and are preferential sites for precipitation,
diffusion and dissolution processes]
iii. at eutectoid temperature, any γ phase present reacts to form two solid as per the
eutectoid reaction [the lamellar structure grows on the prior γ grains]
PHASE DIAGRAMS WITH INTERMEDIATE PHASES
PHASE DIAGRAMS WITH INTERMETALLIC
COMPOUNDS.
• Besides solid solutions, intermetallic compounds, that have precise chemical
compositions can exist in some systems.
• When using the lever rules, intermetallic compounds are treated like any other phase,
except they appear not as a wide region but as a vertical line.
THIS DIAGRAM CAN BE THOUGHT OF AS TWO JOINED EUTECTIC
DIAGRAMS, FOR Mg-Mg2Pb AND Mg2Pb-Pb. IN THIS CASE THE COMPOUND
Mg2Pb CAN BE CONSIDERED AS A COMPONENT.

intermetallic
compound
THE IRON–IRON CARBIDE (FE–FE3C) PHASE DIAGRAM
PHASES IN THE FE–FE3C PHASE DIAGRAM

• Ferrite (Fe-α)
• Austenite (Fe-𝛾)
• Ferrite (Fe-𝛿)

• Fe3C ( Cementite)

• Fe-C (liquid solution

THE END !!!!!