Phase Diagrams and Phase

Transformations

Prof. V. E. Buchanan, School of Engineering

 Learning Outcomes (Part 1)
• State the conditions under which solid solutions are
formed
• State the purpose of phase (equilibrium) diagrams
• Explain the different types of binary phase diagrams
• Describe the associated microstructures at different
points in a phase diagram
• Differentiate between hypoeutectic and
hypereutectic systems
• Use the tie-line to determine, at any temperature-
composition, the phases and their composition.
• Use the lever rule to determine, at any temperature-
composition point, the fraction (or mass) of the
phases
 Content
• Alloy formation
• Solid solution and solubility limit
• Nucleation and grain growth
• Phase Diagrams
• The phase rule
• Types of binary phase diagrams
• Interpretation of phase diagrams
• The Lever rule
• The Iron-Iron Carbide Phase Diagram
• Structures of plain carbon steel
• Hypo- and hypereutectic alloys
• Types of steel and their uses
 Solid Solutions
• A solid solution is a single crystalline phase
consisting of two (or more) chemical species.
• Most engineering metallic materials are solid
solutions, called alloys: solvent and solute
• Solid solutions are of two types:
• Interstitial solid solution
• Substitutional solid solutions
P Both substitutional and Compression

interstitial atoms distort the

crystal lattice affecting the
mechanical and
Tension
electrical/electronic properties.
 Interstitial Solid Solution
• In interstitial solid
solutions, the solute atoms
occupy the interstices
between the solvent
atoms.
• Example, Steel – C solute
atoms in Fe
P Conditions for Interstitial Solid
Solution
< Solute atoms must be smaller
than the space in the solvent
lattice.
< The solute and solvent atoms
should have similar
electronegativity.
 Substitutional Solid Solution
• This refers to a foreign atom that substitutes
for or replaces a parent atom in the crystal.
• The arrangement may be ordered or
disordered
• E.g., Cu-Zn, Cu-Ni, Ni-Fe, Mo-W, Au-Ag

Disordered Ordered
 Conditions for Substitutional
Solid Solution
Hume-Rothery=s Rules of Solid Solubility
1.• The radii of the solute and solvent atoms
must not differ by more than 15%, otherwise
creating substantial lattice distortion.
2.• The solute and solvent atoms should have
similar electronegativity.
• Otherwise, intermetallic compounds may form
• They should be in close proximity in periodic table
3.
• The elements should have the same crystal
structure.
• For appreciable solid solubility, the crystal
structures of the two elements must be identical.
 Conditions for Substitutional
Solid Solution, contd.
• . Valency should be the same for both
elements.
• Maximum solubility occurs when the solvent and
solute have the same valency.
• Generally, a metal of lower valency will have a
greater tendency to dissolve a metal of higher
valency. Example, more Al (valency = 3) can be
dissolved in Ni (valency = 2) than visa versa.

Ni and Cu are
totally miscible in
each other.
 Recap
P Solutions may either be solid, liquid or gas.
P A solid solution is a homogeneous structure formed
when two or more components that are completely
soluble in the liquid state remain dissolved in each
other after solidification.
< The solvent comprises the greater part of the solution.
< The solute comprises the smaller part of the solution.
P Solid solutions are formed substitutionally or
interstitially.
P Every element or compound has a solubility limit of
how much can be dissolved in another element or
compound at a specific temperature and pressure.
P When the solubility limit is exceeded, a second phase
forms in the alloy.
 Terms
• Phase - A homogeneous region in a material that
has different composition or physical
characteristics from another region.
• E.g., Water and ice are the same
substance, H2O, but are different
phases because they have a
different structure.
• Systems with two or more phases are
heterogeneous or mixtures, e.g., ice + water.

• Equilibrium - A system is at equilibrium if its

phases do not change with time, that is, the
system is stable.
 Terms, contd.
• Degrees of freedom - the number of variables
(temperature, pressure, and composition) that
can be changed independently without
changing the phases(s) of the system.
• Gibbs phase rule: If a system contains P
phases and C components is in equilibrium the
number of degrees of freedom F is given by:
P+F=C+2
• The “2" represents any two of the above variables
• For metallurgical systems, pressure has
negligible effect (constant); thus, P + F = C + 1
• For binary alloy systems, P + F = 3
Application of Gibbs Phase Rule
• At Point A
• P+F=3
• 1+2=3
• At Point B
• P+F=3
• 2+1=3
• At Point C
• P+F=3
• 1+2=3
 Terms
• Phase Diagram
A graphical
representation of
the phases in a
system at any
given temperature,
composition, and
pressure. Phase diagram for water
• Phase diagrams are also called Thermal
Equilibrium Diagrams.
• Phase diagrams are determined experimentally by
recording of slow heating and cooling rates over a
range of compositions.
 Importance of Phase Diagrams
• Determine the number, type, composition,
amount of phases present in any given alloy
at a specific temperature.
• Properties of a materials depend on the phases
present, so properties can be changed by altering
these quantities.
• Predict the temperature at which freezing or
melting of an alloy begins or ends.
• Predict the temperature for heat treatments.
• Predict the microstructure of an alloy at a
given temperature.
 Limitations of Phase Diagrams
• They do not indicate the size, shape,
orientation, or distribution of the phases.
• They do not give any information about the
physical and mechanical properties of the
materials.
• They do not indicate the phases produced by
fast cooling rates.
• They only show the equilibrium state of alloys
(i.e., under very slow cooling rates); however,
in normal industrial processes, alloys are
rarely cooled slowly enough to approach
equilibrium.
 Sugar-water Phase Diagram

• At point A
• P+F=C+2
• 1+3=2+2
• At Co = 80%
at 20 oC
• P+F=C+2
• 2+2=2+2

• The solubility limit increases as the

temperature increases.
• F represents the controllable variables.
 Solidification of Metals
1. Nucleation
‚ During solidification, atoms from the
liquid begin to group together and form
tiny crystals (nuclei). Imperfections
serve as nucleation sites, and the
number of nucleation sites depends on
the rate of solidification.
2. Growth
‚ As the metal continues to cool, the
crystals begin to grow in the liquid.
‚ The crystals increase in size until they
impinge upon each other, forming grain
boundaries.
- Fast rcooling - many nuclei, small crystals
- Slow rcooling - few nuclei, large crystals
 Types of Phase Diagrams
• Uninary
• One component
• E.g., Water, Methanol, Aluminium, etc.
• Binary
• Two components
• E.g. Cu-Ni, Ag-Au, Pb-Sn, Al-Pb, Al2O3-Cr2O3, etc.
• Tenary
• Three components
• E.g. Fe-Cr-C
• Quaternary
• Four components
• E.g,. Fe-Cr-C-Ni
 Typical Types of Binary Phase
Diagrams
• Isomorphous
• Two components are completely soluble in each
other in the solid and liquid state at all compositions.
• Eutectic
• Two components are completely soluble in the liquid
state but only partially soluble in the solid state.
• Peritectic
• Systems contains one or more intermediate phases.
• Monotectic
• The two components are completely insoluble in the
liquid and solid state.
 Note!
• The proceeding phase diagrams are for equilibrium
conditions, which involve slow cooling.
• Upon slow heating the transformations will occur in
the reverse manner.
• When alloys are cooled rapidly, entirely different
results are obtained, since there may not be
sufficient time for the normal phase changes to
occur.
• In such cases, the equilibrium phase diagram is no
longer a valid tool for engineering analysis.
• Rapid cooling, however, is important in the heat
treatment of steels and other metals.
 Binary Isomorphous Phase Diagram
• Two components are totally soluble in one another in
the solid and liquid state for all proportions.
• Example, Cu-Ni, Ge-Si, Au-Ag, Al2O3-Cr2O3

• RCu = 0.128 nm and

RNi = 0.125 nm
• Electronegativities of
Cu and Ni are 1.9
and 1.8
• Both are FCC
• Both can have
valencies of 2 Cu-Ni phase diagram
(Hume-Rothery • Between the solidus and liquidus line,
rules). two phases exist: solid and liquid.
 What happens during cooling from
liquid to solid of Cu-Ni alloy?
a For a 35 wt.% Ni-65
wt.% Cu alloy at 1300°C,
complete liquid.
b Solid phases begin to
form from the liquid.
c The solid phases
increase and the liquid
phase decreases.
d Liquid phase is almost
gone.
e Complete solid below the
solidus line.
 Information Available from a
Phase Diagram
• Three most important information are:
• The phases that are present
• The composition of these phases
• The fractions or percentages of the phases
• Other information are:
• Solidus
• Liquidus
• Invariant reactions (point where three phases are
in equilibrium)
• Prediction of the microstructure
 How to Find the Phases Present
• Locate the temperature-composition point on
the diagram and note the phases with which
the corresponding phase field is labelled.

0
C 1455

Liquid (L)
P 70%Cu-30%Ni, 1000 0C
< Single phase, solid
L+α
P 32%Cu-68%Ni, 1320 0C
1085
Solid (α)
< Two phases, Liquid
and Solid
0
0 10 20 30 40 50 60 70 80 90 100 Ni
100 90 80 70 60 50 40 30 20 10 0 Cu

Composition - % weight
 Composition of the Phases
Draw the tie-line (or isotherm) at the desired
temperature, touching the single phase fields.
Drop perpendiculars from the points where the
tie-line meets these fields, and read the phase
composition on the x-axis.
0
C
Tie-line 1455 Example:
Liquid (L) Given T = 1320 0C
L+α
T
L = 72%Cu - 28%Ni
1085
Solid (α) S = 40%Cu - 60%Ni

0
0 10 20 30 40 50 60 70 80 90 100 Ni
100 90 80 70 60 50 40 30 20 10 0 Cu

Composition - % weight
 Fractions of the Phases
• When a single phase exists, the alloy is
completely that phase.
• For a two phase alloy, the Lever Rule is
used.
C0  CL C  CO
f  fL   1  f
C  CL C  CL
CL - composition of liquid phase
CO - composition of alloy
CS - composition of solid phase
 Problem 1
0
C
1455 200 kg of a 60 wt% Cu
Liquid (L)
L+α
- 40 wt% Ni alloy is
1320
heated to a temperature
1085
of 1320 oC. Determine
Solid (α)
the mass of solid and
0
liquid phases.
0 10 20 30 40 50 60 70 80 90 100 Ni
100 90 80 70 60 50 40 30 20 10 0 Cu

Composition - % weight

C0  CL 40  28
fs    0.375
C  CL 60  28 Mass of solid = 0.375 × 200 = 75 kg
Mass of liquid = 0.625 × 200 = 125 kg
C  CO 60  40
fL    0.625
C  CL 60  28
 Binary Eutectic Phase Diagram
• This type contains an
invariant or eutectic
reaction in which the
liquid phase (L)
transforms into a mixture
of two solid phases (α
and β) upon cooling.
• The eutectic reaction is: L183 o
C = α(s) + β(s)
• The α phase is a solid solution of Pb with a small
amount of Sn as the solute. The β phase is a
solid solution of Sn with Pb as the solute.
• At the eutectic point, α, β, and L can coexist.
• Examples are Sn-Pb, Au-Be, Cu-Ag, and Bi-Cd
phase diagrams.
 Properties of a Eutectic Alloy
• It solidifies at a constant fixed temperature
like pure metal.
• It has the lowest melting point alloy in the
series.
• It has a fixed composition.
• The eutectic is commonly lamellar.
• It may be composed of pure metals, solid
solutions and intermediate phases, or a
combination.
• Used for electrical and thermal fuses, in
metal sprayings, and for temperature
measurement
 Lead-Tin Phase Diagram • There is
limited solid
solubility of
each phase
(α and β).
• The eutectic
reaction at
61.9% Sn
and 183 oC is
the most
important
feature of
this system.
• RSn = 0.151 nm, RPb = 0.175 nm, 15.9% diff. Electronegativities
of Sn and Pb are both 1.8. Sn has a BCT crystal structure, while
Pb has the FCC crystal structure. Valencies are +2, +4.
Cooling of Pb-40 wt%Sn alloy under
equilibrium conditions from 300 °C
• Initially there is 100% liquid
solution of 40wt% Sn in Pb.
• At the liquidus, proeutectic α
starts to precipitate, and
grows until the eutectic
temperature is reached.
• As the liquid has reached
the eutectic composition,
61.9 wt% Sn, the remaining
liquid at this point
undergoes the eutectic
reaction, and transforms
into α and β.
Problem 2
 Cu-Ag Phase Diagram

• RCu = 0.128 nm, RAg = 0.144 nm, 12.5% difference.

Electronegativities of Cu and Ag are both 1.9. Both have a
FCC crystal structure. Valences are +1 (Cu), +2(Ag).
 Problem 3
The microstructure of a Cu-Ag alloy at 777ºC
consists of primary α (or proeutectic α) and
eutectic microstructures. If the mass fraction of
the primary α is 0.73, determine the alloy
composition and the total amout of α.
• Note: A primary phase (such as primary α) refers to
the solid phase that precipitates out prior to the
eutectic reaction. It is also called the proeutectic
phase.
• Its amount is the fraction just above the eutectic
temperature, obtained by utilising the tie line.
• Similarly, the fraction of eutectic is equal to the
fraction just above the eutectic temperature.
 Solution 3 • Given a two-phase
region (α + eutectic) at
777 oC.
• The tie line can be
considered to be EB
since 777 oC is just
below the eutectic
temperature.
Ceutectic  C0
  o
 o

f primary  777 C  f primary  779 C  
Ceutectic  C
To find total alpha, the tie
line = BG.
C  Co
f total  (777 C) 
o
719.  C0 C  C
. 
073
719.  80. 
912.  25.25
.  8.0
912
C0  2525
. wt % Ag
 0.79
 Reminder
• The Tie-Line is an isothermal (constant
temperature) line connecting the
compositions of the two phases in a two
phase field.
• It is used to find the compositions of the phases in
the two phase field.
• Each phase will have a unique chemical
composition which will be different from each
other, and will also be different from the overall
composition.
• The Lever Rule is a way in which to calculate
the proportions of each phase present on a
phase diagram in a two phase field at a given
temperature and composition.
 Reminder, contd.
• Solidus
• The highest temperature at which an alloy (of a
given composition) is completely solid
• The temperature at which an alloy (of a given
composition) begins to liquefy
• Liquidus
• The lowest temperature at which an alloy (of a
given composition) is completely liquid
• The temperature at which at which an alloy (of a
given composition) begins to solidify
• Solvus
• A line which separates a solid phase from another
solid phase, intermediate phase or intermetallic
compound.
 Last week
We discussed two types of binary phase
diagrams:

Isomorphous Eutectic
Next is the Peritectic type
 Peritectic Type Phase Diagram
• In this type the phase diagram contains a peritectic
reaction.
• Peritectic reaction : L + α(s) = β(s)
• In the peritectic reaction, a liquid (L) and a solid (α)
transform into another solid (β) on cooling.
• This type also contains intermediate phases and
intermetallic compounds:
• Intermediate phase: a phase whose composition range
is between those of terminal phases.
• Intermetallic compound: has a fixed composition, such
as Fe3C
• The phase diagrams may be more complex, but every
region contains either one or two phases. As such, the
lever rule can be used to calculate the fraction of each
phase in the two-phase regions.
Intermediate phase and Intermetallic
compound

In the Cu-Zn phase diagram, α In the Mg-Pb system

and η are terminal phases, and the intermetallic
β, γ, and ε are intermediate compound Mg2Pb
phases. appears as a vertical
line (isoplex) at 81%.
Fe-Fe3C Phase Diagram
 Learning Outcomes
• Describe the invariant reactions in the iron-
iron carbide (Fe-Fe3C) phase diagram
• Describe the associated microstructures at
different points in the Fe-Fe3C phase
diagram
• Differentiate between hypoeutectoid and
hypereutectoid systems
• Use the tie-line to determine the phases and
their composition
• Use the lever rule to determine the fraction
(or mass) of the phases
• Differentiate between the classes of steels
 Invariant Reactions in the Fe-Fe3C System
Note: The three horizontal lines on the Fe-C phase
diagram indicate the isothermal reactions (on cooling /
heating) for the three reactions.
• Peritectic: L + δ W γ
• Occurs at 1493 oC, with low 0.16 wt% C (almost
no engineering importance).
• Eutectic: L W γ + Fe3C
• Occurs at 1147 oC, with 4.3 wt% C
• Called cast irons.
• Eutectoid: γ W α + Fe3C
• Occurs at 727 oC with eutectoid composition of 0.8
wt% C, into a two-phase mixture (ferrite &
cementite).
 Solid Phases in the Fe-Fe3C System
• Ferrite (α)
• An interstitial solid solution of
carbon in BCC iron
• Stable form of iron below 912 oC
and it dissolves only 0.008% C
at room temperature.
• BCC crystal structure,
ferromagnetic
• Maximum solubility limit is 0.02%
C at 727 oC
• It is the softest structure that
appears on the phase diagram.
 Austenite (γ)
• An interstitial solid solution of
carbon in FCC iron
• Maximum solubility limit is
o
2.1% C at 1147 C
• FCC crystal structure
• Not stable below 727 oC except
under certain conditions
• Tough, ductile, high formability, non
magnetic, and stronger than pearlite
• Most heat treatments begin with this single
phase.
 Pearlite
• A laminated structure of
ferrite (88%) and cementite
(12%)
• The white ferritic matrix
contains thin plates of
cementite (dark).
• This eutectoid mixture
contains 0.8% C and is
formed at 727 °C on very
slow cooling.
• Harder and stronger than
ferrite, but softer and more
ductile than cementite.
 Cementite (Fe3C)
• Intermetallic compound of
iron & carbon, as Fe3C (Fe-
6.67% C)
• It is the hardest structure that
appears on the phase
diagram.
• Orthorhombic crystal structure
• Very hard and brittle
• Low tensile strength and high compressive
strength
• Metastable (but remains as a compound
indefinitely at room temperature)
 Ledeburite
• Eutectic mixture of austenite (52%) and
cementite (48%).
• Contains 4.3% C and is formed at 1147 °C.
Most often used section of the Fe-
Fe3C Phase Diagram
Typical Microstructural
Transformations
 Explanation - Eutectoid Steel
• Consider a 0.8% C steel (eutectoid composition),
being slow cooled from the austenite state, the 0.8%
C being dissolved in solid solution within the FCC.
• When the steel cools through 723 °C, several
changes occur simultaneously.
• The iron wants to change crystal structure from the
FCC austenite to the BCC ferrite, but the ferrite can
only contain 0.02% carbon in solid solution.
• The excess carbon is rejected and forms the carbon-
rich intermetallic known as cementite.
• The net reaction at the eutectoid is the formation of
the pearlite structure - the Fe3C and the
transformation of the remaining austenite into ferrite.
 Explanation - Hypoeutectoid Steel
• Consider a 0.4 % C steel. At high temperature the
material is entirely austenite.
• Upon cooling it enters a region where the stable
phases are ferrite and austenite.
• The low-carbon ferrite nucleates and grows, leaving
the remaining austenite richer in carbon.
• At 727 °C, the remaining austenite will have
assumed the eutectoid composition (0.8% C), and
further cooling transforms it to pearlite.
• The resulting structure is a mixture of primary or
pro-eutectoid ferrite (ferrite that forms above the
eutectoid temperature) and pearlite.
 Explanation - Hypereutectoid Steel
• Consider a 1.2% C steel. At high temperatures the
material is entirely austenite.
• Upon cooling it enters a region where the stable
phases are austenite and cementite.
• The solubility of carbon in austenite decreases,
causing cementite to form and grow until the
temperature reaches the eutectoid point (727 °C).
• The remaining austenite transforms to pearlite upon
slow cooling through the eutectoid temperature.
• The resulting structure consists of primary cementite
and pearlite.
• The continuous network of primary cementite will
cause the material to be extremely brittle.
 What happens when alloys are not
cooled slowly?
• When the alloys are cooled rapidly, entirely
different results are obtained, since sufficient
time may not be provided for the normal
phase reactions to occur.
• In these cases, the equilibrium phase
diagram is no longer a valid tool for
engineering analysis.
• However, rapid-cool processes are important
in the heat treatment of steels and other
metals (see lecture on Heat Treatment)
 More on Steel
• Steel is an alloy of iron that contains carbon
ranging by weight between 0.02% and 2.1%
• It often includes other alloying ingredients,
such as Mn, Cr, Ni, Mo, Va, Co, Si and Ti to
enhance properties such as machinability,
wear resistance, strength, and toughness.
• Steels may be classified as:
• Plain carbon steel
• Low-carbon (<0.2%), medium-carbon (0.2%< and
<0.5%), high-carbon (>0.5%).
• Low-alloy steel - Cr, Mn, Mo, Ni, V, etc.
• Stainless steel - highly alloyed steels, Cr 15%, Ni
• Tool steel - highly alloyed steels designed for use
as industrial cutting tools, dies, and moulds.
Mechanical Behaviour of Fe-C
Alloys
• Cementite is
harder and more
brittle than ferrite
• Increasing
cementite fraction
therefore makes
harder, less
ductile material.

Callister, 2007
 Problem 4
• For a Fe-0.35 wt% C alloy, and at a
temperature just below the eutectoid
temperature, determine the following:
• (a) the fractions of total ferrite and cementite
phases
• (b) the fractions of pro-eutectoid ferrite and
pearlite
• (c) the fraction of eutectoid ferrite
 Solution 4
CFe3C  Co 667
.  035
(a) f 727 C  

tie
 o
 
CFe3C  C 667
.
.  002
.
 095
.

f FetieC  1  095
.  005
.
3

CE  Co 08.  035
.
(b) f tie
pro  eutectoid   o

 f  727 C   
CE  C 08.  002
.
 058
.

f Pearlite  1  058
tie
.  042
.
(c) f eutectoid   095
.  058
.  037
.
Note: Pearlite has 88% α = 0.88 × 0.42 = 0.37
 Problem 5
Consider 2.5 kg of plain
carbon steel containing 1.2
wt% C, cooled to just below
727ºC.

a) What is the pro-eutectoid

phase?
b) How many kg each of
ferrite and cementite forms?
c) How many kg each of
pearlite and the pro-eutectoid
phase forms?
 Solution 5
(a)The pro-eutectoid phase forms prior to the
eutectoid reaction, so it is the Fe3C (cementite) phase.

(b)

(c)
 Bibliography/References
• William D. McCallister, Jr., Materials Science
and Engineering - An Introduction, 7th ed.,
John Wiley & Sons, Inc., New York, 2007
• http://users.fs.cvut.cz/libor.benes/vyuka/mats
cienceii/ironcarbondiapresentation-
130312054611-phpapp01.ppt