Chapter Outline: Phase Diagrams Definitions: Components and Phases

Microstructure and Phase Transformations in Component - chemically recognizable species (Fe and C
Multicomponent Systems in carbon steel, H2O and Sucrose in sugar solution in
water). A binary alloy contains two components, a ternary
alloy – three, etc.
ƒ Definitions and basic concepts Phase – a portion of a system that has uniform physical
ƒ Phases and microstructure and chemical characteristics. Two distinct phases in a
system have distinct physical and/or chemical
ƒ Binary isomorphous systems (complete solid solubility) characteristics (e.g. water and ice, water and oil) and are
separated from each other by definite phase boundaries. A
ƒ Binary eutectic systems (limited solid solubility)
phase may contain one or more components.
ƒ Binary systems with intermediate phases/compounds
A single-phase system is called homogeneous,
ƒ The iron-carbon system (steel and cast iron)
systems with two or more phases are mixtures or
heterogeneous systems.

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Definitions: Solubility Limit Microstructure

Solvent - host or major component in solution, solute - The properties of an alloy depend not only on proportions
minor component. of the phases but also on how they are arranged structurally
at the microscopic level. Thus, the microstructure is
Solubility Limit of a component in a phase is the specified by the number of phases, their proportions, and
maximum amount of the component that can be dissolved their arrangement in space.
in it (e.g. alcohol has unlimited solubility in water, sugar
has a limited solubility, oil is insoluble). The same
concepts apply to solid phases: Cu and Ni are mutually Microstructure of cast Iron
soluble in any amount (unlimited solid solubility), while C
has a limited solubility in Fe.

http://www2.umist.ac.uk/material/research/intmic/ (link is dead)

The long gray regions are flakes of graphite.

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

Phase diagrams will help us to understand and predict

microstructures like the one shown in this page
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 Equilibrium and Metastable States Phase diagram
Phase diagram is a graphical representation of all the
A system is at equilibrium if at constant temperature,
equilibrium phases as a function of temperature, pressure,
pressure and composition the system is stable, not
and composition.
changing with time.
For one component systems, the equilibrium state of the
Equilibrium is the state that is achieved given sufficient system is defined by two independent parameters (P and
time. But the time to achieve equilibrium may be very long T), (T and V), or (P and V).
(the kinetics can be slow) that a state along the path to the
equilibrium may appear to be stable. This is called a Pressure-temperature phase diagram for H2O:
metastable state.

In thermodynamics the equilibrium is described as a state of a

system that corresponds to the minimum of thermodynamic
function called the free energy. Thermodynamics tells us that:
• Under conditions of a constant temperature and pressure and
composition, the direction of any spontaneous change is
toward a lower free energy.
• The state of stable thermodynamic
Free Energy

equilibrium is the one with equilibrium

minimum free energy.
• A system at a metastable state is
trapped in a local minimum of free
energy that is not the global one.
metastable
Arrangement of atoms
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PVT surface of a pure (1-component) substance A pure substance is heated at constant pressure

Tb

http://www.eng.usf.edu/~campbell/ThermoI/ThermoI_mod.html
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 Pressure-temperature phase diagram for carbon 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 is also a variable.
We will limit our discussion of phase diagrams of multi-
component systems to binary alloys and will assume
pressure to be constant at one atmosphere. Phase diagrams
for materials with more than two components are complex
and difficult to represent. An example of a phase diagram
for a ternary alloy is shown for a fixed T and P below.

ternary phase diagram

of Ni-Cr-Fe

We can see graphite, diamond, liquid carbon on the phase

diagram… but where are fullerenes and nanotubes?

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Binary Isomorphous Systems (I) Binary Isomorphous Systems (II)

Isomorphous system - complete solid solubility of the two Example of isomorphous system: Cu-Ni (the complete
components (both in the liquid and solid phases). solubility occurs because both Cu and Ni have the same
crystal structure, FCC, similar radii and electronegativity).

α+L

Three phase region can be identified on the phase diagram:

Liquid (L) , solid + liquid (α +L), solid (α )
Liquidus line separates liquid from liquid + solid
Solidus line separates solid from liquid + solid
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 Binary Isomorphous Systems (III) Interpretation of a binary phase diagrams
In one-component system melting occurs at a well-defined For a given temperature and composition we can use phase
melting temperature. diagram to determine:
In multi-component systems melting occurs over the range 1) The phases that are present
of temperatures, between the solidus and liquidus lines.
Solid and liquid phases are at equilibrium with each other 2) Compositions of the phases
in this temperature range. 3) The relative fractions of the phases

Finding the composition in a two phase region:

Liquidus
1. Locate composition and temperature in diagram
L
Temperature

liquid solution
2. In two phase region draw the tie line or isotherm
α+L
3. Note intersection with phase boundaries. Read
compositions at the intersections.
Solidus
liquid solution The liquid and solid phases have these compositions.
α +
crystallites of
solid solution

A 20 40 60 80 B
polycrystal
solid solution Composition, wt %

Xliquid
B
XB Xsolid
B

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The lever rule Derivation of the lever rule

Finding the amounts of phases in a two phase region:
1) All material must be in one phase or the other:
1. Locate composition and temperature in diagram
Wα + W L = 1
2. In two phase region draw the tie line or isotherm
3. Fraction of a phase is determined by taking the length 2) Mass of a component that is present in both phases
of the tie line to the phase boundary for the other
equal to the mass of the component in one phase +
phase, and dividing by the total length of tie line
mass of the component in the second phase:
WαCα + WLCL = Co
α α+β
β 3) Solution of these equations gives us the lever rule.

WL = (Cα - Co) / (Cα - CL)

Wα = (Co - CL) / (Cα - CL)

Wα Wβ

The lever rule is a mechanical analogy to the mass balance

calculation. The tie line in the two-phase region is
analogous to a lever balanced on a fulcrum.

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 Phase compositions and amounts. An example. Development of microstructure in isomorphous alloys
Equilibrium (very slow) cooling

Co = 35 wt. %, CL = 31.5 wt. %, Cα = 42.5 wt. %

Mass fractions:
WL = S / (R+S) = (Cα - Co) / (Cα - CL) = 0.68

Wα = R / (R+S) = (Co - CL) / (Cα - CL) = 0.32

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Development of microstructure in isomorphous alloys Development of microstructure in isomorphous alloys

Equilibrium (very slow) cooling Fast (non-equilibrium) cooling

¾ Solidification in the solid + liquid phase occurs

gradually upon cooling from the liquidus line.

¾ The composition of the solid and the liquid change

gradually during cooling (as can be determined by the
tie-line method.)

¾ Nuclei of the solid phase form and they grow to

consume all the liquid at the solidus line.

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 Development of microstructure in isomorphous alloys Binary Eutectic Systems (I)
Fast (non-equilibrium) cooling systems (alloys) with limited solubility
• Compositional changes require diffusion in solid and
liquid phases

• Diffusion in the solid state is very slow. ⇒ The new

layers that solidify on top of the existing grains have the
equilibrium composition at that temperature but once
they are solid their composition does not change. ⇒
Formation of layered (cored) grains and the invalidity of
the tie-line method to determine the composition of the
solid phase.

• The tie-line method still works for the liquid phase,

where diffusion is fast. Average Ni content of solid
grains is higher. ⇒ Application of the lever rule gives
us a greater proportion of liquid phase as compared to
the one for equilibrium cooling at the same T. ⇒ Credit: Kenneth A. Jackson, University of Arizona.
Solidus line is shifted to the right (higher Ni contents),
solidification is complete at lower T, the outer part of
the grains are richer in the low-melting component (Cu).

• Upon heating grain boundaries will melt first. This can

lead to premature mechanical failure.

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Binary Eutectic Systems (II) Binary Eutectic Systems (III)

Lead – Tin phase diagram

Liquidus
liquid
Solidus
Temperature, °C
Temperature, °C

Invariant or eutectic point

Solvus
α+β Eutectic isotherm
Copper – Silver phase diagram

Composition, wt% Ag Composition, wt% Sn

Three single phase regions (α - solid solution of Ag in Cu

Eutectic or invariant point - Liquid and two solid phases
matrix, β = solid solution of Cu in Ag matrix, L - liquid)
co-exist in equilibrium at the eutectic composition CE and
Three two-phase regions (α + L, β +L, α +β) the eutectic temperature TE.
Solvus line separates one solid solution from a mixture of
Eutectic isotherm - the horizontal solidus line at TE.
solid solutions. Solvus line shows limit of solubility

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 Binary Eutectic Systems (IV) Binary Eutectic Systems (V)

Compositions and relative amounts of phases are

Eutectic reaction – transition between liquid and mixture
determined from the same tie lines and lever rule, as for
of two solid phases, α + β at eutectic concentration CE.
isomorphous alloys
The melting point of the eutectic alloy is lower than that of
the components (eutectic = easy to melt in Greek).

At most two phases can be in equilibrium within a phase •A

field. Three phases (L, α, β) may be in equilibrium only
at a few points along the eutectic isotherm. Single-phase
regions are separated by 2-phase regions. •B

•C

For points A, B, and C calculate the compositions (wt. %)

and relative amounts (mass fractions) of phases present.

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Development of microstructure in eutectic alloys (I) Development of microstructure in eutectic alloys (II)

Several different types of microstructure can be formed in At compositions between the room temperature solubility
slow cooling an different compositions. limit and the maximum solid solubility at the eutectic
temperature, β phase nucleates as the α solid solubility is
Let’s consider cooling of liquid lead – tin system at exceeded upon crossing the solvus line.
different compositions.

L
In this case of lead-rich
alloy (0-2 wt. % of tin)
solidification proceeds in
α +L
the same manner as for
isomorphous alloys (e.g. α
Cu-Ni) that we discussed
earlier.
α +β

L → α +L→ α

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 Development of microstructure in eutectic alloys (III) Development of microstructure in eutectic alloys (IV)
Solidification at the eutectic composition Solidification at the eutectic composition

No changes above the eutectic temperature TE. At TE the Compositions of α and β phases are very different →
liquid transforms to α and β phases (eutectic reaction). eutectic reaction involves redistribution of Pb and Sn atoms
by atomic diffusion. This simultaneous formation of α and
β phases result in a layered (lamellar) microstructure that is
called eutectic structure.

Formation of the eutectic structure in the lead-tin system.

In the micrograph, the dark layers are lead-reach α phase, the
L → α +β light layers are the tin-reach β phase.

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Development of microstructure in eutectic alloys (V) Development of microstructure in eutectic alloys (VI)
Compositions other than eutectic but within the range of
the eutectic isotherm Microconstituent – element of the microstructure having a
distinctive structure. In the case described in the previous
Primary α phase is formed in the α + L region, and the page, microstructure consists of two microconstituents,
eutectic structure that includes layers of α and β phases primary α phase and the eutectic structure.
(called eutectic α and eutectic β phases) is formed upon
crossing the eutectic isotherm.
L → α + L → α +β

Although the eutectic structure consists of two phases, it is

a microconstituent with distinct lamellar structure and
fixed ratio of the two phases.
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 How to calculate relative amounts of microconstituents? How to calculate the total amounts of phases?

Eutectic microconstituent forms from liquid having eutectic Fraction of α phase determined by application of the lever
composition (61.9 wt% Sn)
rule across the entire α + β phase field:
We can treat the eutectic as a separate phase and apply the
lever rule to find the relative fractions of primary α phase Wα = (Q+R) / (P+Q+R) (α phase)
(18.3 wt% Sn) and the eutectic structure (61.9 wt% Sn):
Wβ = P / (P+Q+R) (β phase)
We = P / (P+Q) (eutectic) Wα’ = Q / (P+Q) (primary)

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Phase diagrams with intermediate phases Phase diagrams with intermetallic compounds
Eutectic systems that we have studied so far have only two Besides solid solutions, intermetallic compounds, that
solid phases (α and β) that exist near the ends of phase have precise chemical compositions can exist in some
diagrams. These phases are called terminal solid systems.
solutions. When using the lever rules, intermetallic compounds are
Some binary alloy systems have intermediate solid treated like any other phase, except they appear not as a
solution phases. In phase diagrams, these phases are wide region but as a vertical line.
separated from the composition extremes (0% and 100%).
Example: in Cu-Zn, α and η are terminal solid solutions,
β, β’, γ, δ, ε are intermediate solid solutions.

intermetallic
compound

This diagram can be thought of as two joined eutectic

diagrams, for Mg-Mg2Pb and Mg2Pb-Pb. In this case
compound Mg2Pb can be considered as a component.
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 Eutectoid Reactions (I) Eutectic and Eutectoid Reactions
The eutectoid (eutectic-like in Greek) reaction is similar to
the eutectic reaction but occurs from one solid phase to two Temperature
new solid phases. l

Invariant point (the eutectoid) – three solid phases are in

equilibrium. γ +l
γ l +β
Eutectic
Upon cooling, a solid phase transforms into two other solid temperature
phases (δ ↔ γ + ε in the example below) γ +β
α+γ
Eutectoid α β
Looks as V on top of a horizontal tie line (eutectoid temperature
isotherm) in the phase diagram. α+β

Cu-Zn Eutectoid Eutectic

composition composition
Composition

The above phase diagram contains both an eutectic reaction

and its solid-state analog, an eutectoid reaction
Eutectoid

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Peritectic Reactions Congruent phase transformations

A peritectic reaction - solid phase and liquid phase will A congruent transformation involves no change in
together form a second solid phase at a particular composition (e.g., allotropic transformation such as α-Fe to
temperature and composition upon cooling, e.g. L + α ↔ β γ-Fe or melting transitions in pure solids).

These reactions are rather slow as the product phase will For an incongruent transformation, at least one phase
form at the boundary between the two reacting phases thus changes composition (e.g. eutectic, eutectoid, peritectic
separating them, and slowing down any further reaction. reactions).

Congruent Ni-Ti
melting of γ
Temperature

α + liquid liquid

α +β
β β + liquid

Peritectics are not as common as eutectics and eutectiods,

but do occur in some alloy systems. There is one in the Fe-
C system that we will consider later.

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 The Iron–Iron Carbide (Fe–Fe3C) Phase Diagram Phases in Fe–Fe3C Phase Diagram

In their simplest form, steels are alloys of Iron (Fe) and ¾ α-ferrite - solid solution of C in BCC Fe
Carbon (C). The Fe-C phase diagram is a fairly complex • Stable form of iron at room temperature.
one, but we will only consider the steel part of the diagram, • The maximum solubility of C is 0.022 wt%
up to around 7% Carbon.
• Transforms to FCC γ-austenite at 912 °C
¾ γ-austenite - solid solution of C in FCC Fe
• The maximum solubility of C is 2.14 wt %.
• Transforms to BCC δ-ferrite at 1395 °C
• Is not stable below the eutectoid temperature
(727 ° C) unless cooled rapidly (Chapter 10)
¾ δ-ferrite solid solution of C in BCC Fe
• The same structure as α-ferrite
• Stable only at high T, above 1394 °C
• Melts at 1538 °C
¾ Fe3C (iron carbide or cementite)
• This intermetallic compound is metastable, it
remains as a compound indefinitely at room T, but
decomposes (very slowly, within several years)
into α-Fe and C (graphite) at 650 - 700 °C
¾ Fe-C liquid solution

MSE 2090: Introduction to Materials Science Chapter 9, Phase Diagrams 41 MSE 2090: Introduction to Materials Science Chapter 9, Phase Diagrams 42

A few comments on Fe–Fe3C system Classification. Three types of ferrous alloys

C is an interstitial impurity in Fe. It forms a solid solution ¾ Iron: less than 0.008 wt % C in α−ferrite at room T
with α, γ, δ phases of iron
¾ Steels: 0.008 - 2.14 wt % C (usually < 1 wt % )
Maximum solubility in BCC α-ferrite is limited (max. α-ferrite + Fe3C at room T
0.022 wt% at 727 °C) - BCC has relatively small interstitial
positions Examples of tool steel (tools for cutting other metals):
Fe + 1wt % C + 2 wt% Cr
Maximum solubility in FCC austenite is 2.14 wt% at 1147 Fe + 1 wt% C + 5 wt% W + 6 wt % Mo
°C - FCC has larger interstitial positions Stainless steel (food processing equipment, knives,
petrochemical equipment, etc.): 12-20 wt% Cr, ~$1500/ton
Mechanical properties: Cementite is very hard and brittle -
can strengthen steels. Mechanical properties also depend
¾ Cast iron: 2.14 - 6.7 wt % (usually < 4.5 wt %)
on the microstructure, that is, how ferrite and cementite are
mixed. heavy equipment casing

Magnetic properties: α -ferrite is magnetic below 768 °C,

austenite is non-magnetic

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 Eutectic and eutectoid reactions in Fe–Fe3C Development of Microstructure in Iron - Carbon alloys

Eutectic: 4.30 wt% C, 1147 °C Microstructure depends on composition (carbon

content) and heat treatment. In the discussion below we
L ↔ γ + Fe3C consider slow cooling in which equilibrium is maintained.
Microstructure of eutectoid steel (I)

Eutectoid: 0.76 wt%C, 727 °C

γ(0.76 wt% C) ↔ α (0.022 wt% C) + Fe3C
Eutectic and eutectoid reactions are very important in
heat treatment of steels
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Microstructure of eutectoid steel (II) Microstructure of hypoeutectoid steel (I)

When alloy of eutectoid composition (0.76 wt % C) is Compositions to the left of eutectoid (0.022 - 0.76 wt % C)
cooled slowly it forms perlite, a lamellar or layered hypoeutectoid (less than eutectoid -Greek) alloys.
structure of two phases: α-ferrite and cementite (Fe3C)
γ → α + γ → α + Fe3C
The layers of alternating phases in pearlite are formed for
the same reason as layered structure of eutectic structures:
redistribution C atoms between ferrite (0.022 wt%) and
cementite (6.7 wt%) by atomic diffusion.
Mechanically, pearlite has properties intermediate to soft,
ductile ferrite and hard, brittle cementite.

In the micrograph, dark areas are

Fe3C layers, light phase is α-ferrite

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 Microstructure of hypoeutectoid steel (II) Microstructure of hypereutectoid steel (I)
Hypoeutectoid alloys contain proeutectoid ferrite (formed Compositions to the right of eutectoid (0.76 - 2.14 wt % C)
above the eutectoid temperature) plus the eutectoid perlite hypereutectoid (more than eutectoid -Greek) alloys.
that contain eutectoid ferrite and cementite.
γ → γ + Fe3C → α + Fe3C

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Microstructure of hypereutectoid steel Microstructure of hypereutectoid steel (II)

Hypereutectoid alloys contain proeutectoid cementite
(formed above the eutectoid temperature) plus perlite that
contain eutectoid ferrite and cementite.

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 How to calculate the relative amounts of proeutectoid Example for hypereutectoid alloy with composition C1
phase (α or Fe3C) and pearlite?
Fraction of pearlite:
Application of the lever rule with tie line that extends from
the eutectoid composition (0.75 wt% C) to α – (α + Fe3C) WP = X / (V+X) = (6.7 – C1) / (6.7 – 0.76)
boundary (0.022 wt% C) for hypoeutectoid alloys and to (α
+ Fe3C) – Fe3C boundary (6.7 wt% C) for hipereutectoid Fraction of proeutectoid cementite:
alloys.
WFe3C = V / (V+X) = (C1 – 0.76) / (6.7 – 0.76)

Fraction of α phase is determined by application of the

lever rule across the entire (α + Fe3C) phase field.
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The Gibbs phase rule The Gibbs phase rule – example of a binary system
Let’s consider a simple one-component system.
F = C − Ph + 2
In the areas where only one P liquid P = const
phase is stable both pressure solid
and temperature can be
independently varied without F = C − Ph + 1
gas
upsetting the phase
equilibrium → there are 2 C=2
degrees of freedom. T

Along the lines where two phases coexist in equilibrium, F = 3 − Ph

only one variable can be independently varied without
upsetting the two-phase equilibrium (P and T are related by
the Clapeyron equation) → there is only one degree of
freedom. ¾ In one-phase regions of the phase diagram T and XB can
be changed independently.
At the triple point, where solid liquid and vapor coexist any
change in P or T would upset the three-phase equilibrium ¾ In two-phase regions, F = 1. If the temperature is
→ there are no degrees of freedom. chosen independently, the compositions of both
In general, the number of degrees of freedom, F, in a phases are fixed.
system that contains C components and can have Ph phases
is given by the Gibbs phase rule: ¾ Three phases (L, α, β) are in equilibrium only at the
F = C − Ph + 2 eutectic point in this two component system (F = 0).

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 Summary
Make sure you understand language and concepts:
¾ Austenite ¾ Microconstituent
¾ Cementite ¾ Pearlite
¾ Component ¾ Peritectic reaction
¾ Congruent transformation ¾ Phase
¾ Equilibrium ¾ Phase diagram
¾ Eutectic phase ¾ Phase equilibrium
¾ Eutectic reaction ¾ Primary phase
¾ Eutectic structure ¾ Proeutectoid cementite
¾ Eutectoid reaction ¾ Proeutectoid ferrite
¾ Ferrite ¾ Solidus line
¾ Gibbs phase rule ¾ Solubility limit
¾ Hypereutectoid alloy ¾ Solvus line
¾ Hypoeutectoid alloy ¾ System
¾ Intermediate solid solution ¾ Terminal solid solution
¾ Intermetallic compound ¾ Tie line
¾ Invariant point
¾ Isomorphous
¾ Lever rule
¾ Liquidus line
¾ Metastable

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