MATERIAL SCIENCE AND ENGINEERING

Course No. : CHE F243

Instructor-in-charge : Nandini Bhandaru
Instructors : Karthik Chethan V., Nandini Bhandaru

1
Phase Diagrams
 Terminology and basic concepts
 Phases and microstructure
 Phase Equilibria and Unary phase diagram
 Binary isomorphous systems (complete solid
solubility)
 Binary eutectic systems (limited solid solubility)
 Binary systems with intermediate phases/compounds
 The iron-carbon system (steel and cast iron)

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Components and Phases
• Components:
The elements or compounds which are present in the alloy
(e.g., Al and Cu)
• Phases:
The physically and chemically distinct material regions
that form (e.g., a and b).

Aluminum- b (lighter
Copper
phase)
Alloy

a (darker
phase)

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Components and Phases
• Component - chemically recognizable species (Fe and C in carbon steel,
H2O and Sucrose in sugar solution in water).
• A binary alloy contains two components, a ternary alloy – three, etc.
• 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
(crystalline phases).
• A phase may contain one or more components.
• Homogeneous and heterogeneous systems.

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Phase Tidbits

• If I mix oil and water, I have two components and two

phases.
• If I put some tin into molten lead and if they are
miscible, I have two components and one phase.
• Water is an example of a one-component system.

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Phase Tidbits
• If I put salt in water, I once again have two
components. You might argue that when I dissolve salt
in water I have only one component: salt water. What
I have is one phase; there are still two components.
• Argument (emulsions and colloids)
• What if I put in too much salt? It begins to precipitate
out and I get two phases, but in both instances I have
two components: the salt and the water.

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Phase Equilibria
Equilibrium

• Solution – solid, liquid, or gas solutions, single phase

• Mixture – more than one phase
Sugar/Water Phase Diagram
100
Solubility
Temperature (ºC)

80 Limit L
(liquid)
60 +
L
40 (liquid solution S
i.e., syrup) (solid
20 sugar)

0 20 40 6065 80 100

Sugar
Water

C = Composition (wt% sugar)

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Effect of T & Composition (Co)
• Changing T can change # of phases: path A to B.
• Changing Co can change # of phases: path B to D.
B (100°C,70) D (100°C,90)
1 phase 2 phases
100

80 L
Temperature (°C)

(liquid)
water- 60 +
L
sugar S
system 40
(liquid solution (solid
i.e., syrup) sugar)
20 A (20°C,70)
2 phases
0
0 20 40 60 70 80 100
Co =Composition (wt% sugar)
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Metastable State
Equilibrium = minimum in the free energy.

Metastable  Equilibrium

Microstructure: Properties of an alloy depend on proportions of the

phases and on how they are arranged at the microscopic level. (number
of phases, their proportions, and their arrangements)

iron–chromium alloy microstructure of a lead–tin alloy

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Microstructure (microscopic features)

• 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, composition, size,
geometry, orientation and their arrangement in
space (stacking or dispersed).
• Needles in a hay stack.

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Identify Features

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Phase Diagram

• Phase diagram is a graphical representation of all the

equilibrium phases as a function of temperature,
pressure, and composition (diffusional constraint
phase diagram).
• 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).

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Usefulness of Phase Diagrams
•Regions
•Phases
•Composition
•Microstructure
•Related properties

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14
15
Phase Diagram of Iron

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Binary Phase Diagrams

• When we combine two elements...

what is the resulting equilibrium state?
• In particular, if we specify...
-- the composition (e.g., wt% Cu - wt% Ni), and
-- the temperature (T)
then...
How many phases form?
What is the composition of each phase?
What is the amount of each phase?

Phase A Phase B

Nickel atom
Copper atom 17
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.

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Binary Isomorphous Systems
• Isomorphous system - complete solid solubility of the two components
(both in the liquid and solid phases).

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Melting point depression and freezing point
elevation

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Information

•For a given temperature and composition we

can use phase diagram to determine:
1) The phases that are present
2) Compositions of the phases
3) The relative fractions of the phases

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Criteria for Solid Solubility

Simple system (e.g., Ni-Cu solution)

Crystal electroneg r (nm)

Structure
Ni FCC 1.9 0.1246
Cu FCC 1.8 0.1278

• Both have the same crystal structure (FCC) and have

similar electronegativities and atomic radii (W. Hume –
Rothery rules) suggesting high mutual solubility.
• Ni and Cu are totally soluble in one another for all proportions.

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Imperfections in Solids

Conditions for substitutional solid solution (S.S.)

• W. Hume – Rothery rule
• 1. r (atomic radius) < 15%
• 2. Proximity in periodic table
• i.e., similar electronegativities
• 3. Same crystal structure for pure metals
• 4. Valency (oxidation states)
• All else being equal, a metal will have a greater tendency to
dissolve a metal of higher valency than one of lower
valency

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Binary Phase Diagrams
T(ºC)
1600

1500 L (liquid)

1400
Phase
Diagram
for Cu-Ni 1300
system
1200 a
(FCC solid
1100
solution)
1000
0 20 40 60 80 100 wt% Ni
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Binary Phase Diagrams

• Rule 1: If we know T and Co, then we know:

-- which phase(s) is (are) present.
T(ºC)
• Examples: 1600
A(1100ºC, 60 wt% Ni): L (liquid)
1 phase: a

B (1250ºC,35)
1500
Cu-Ni
B(1250ºC, 35 wt% Ni): 1400 phase
2 phases: L + a diagram
1300 a
(FCC solid
1200
solution)
1100 A(1100ºC,60)

1000
0 20 40 60 80 100 wt% Ni
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Binary Phase Diagrams
• Rule 2: If we know T and C0, then we can determine:
-- the composition of each phase. Cu-Ni
T(ºC) system
• Examples:
TA A
Consider C0 = 35 wt% Ni tie line
At TA = 1320ºC: 1300 L (liquid)
Only Liquid (L) present B
CL = C0 ( = 35 wt% Ni) TB
a
At TD = 1190ºC:
1200 D (solid)
Only Solid (a) present TD
Ca = C0 ( = 35 wt% Ni)
20 3032 35 4043 50
At TB = 1250ºC: CL C0 Ca wt% Ni
Both a and L present
CL = C liquidus ( = 32 wt% Ni)
Ca = C solidus ( = 43 wt% Ni)
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Binary Phase Diagrams

• Rule 3: If we know T and C0, then can determine:

-- the weight fraction of each phase. Cu-Ni
• Examples: T(ºC) system
Consider C0 = 35 wt% Ni TA A
tie line
At TA : Only Liquid (L) present 1300 L (liquid)
WL = 1.00, Wa = 0 B
At TD : Only Solid ( a) present TB R S
a
WL = 0, Wa = 1.00
1200 D (solid)
At TB : Both a and L present TD
S 43  35
WL 
20 3032 35 40 43 50
  0.73 CL C 0 Ca wt% Ni
R +S 43  32

R
Wa  = 0.27
R +S
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Binary Phase Diagrams
The Lever Rule
• Tie line – connects the phases in equilibrium with each
other – also sometimes called an isotherm
T(ºC) What fraction of each phase?
tie line
Think of the tie line as a lever
1300 L (liquid)
(teeter-totter)
B
TB ML Ma
a
1200 (solid)
R S

20 30CL R S
C0 40 Ca 50

wt% Ni Ma x S  ML x R
Adapted from Fig. 9.3(b),
Callister & Rethwisch 8e.

ML S C  C0 R C  CL
WL    a Wa   0
M L  M a R  S C a  CL R  S C a  CL
 28
Development of microstructure in isomorphous
alloys [Equilibrium (very slow) cooling]
• Phase diagram: T(ºC) L (liquid) L: 35wt%Ni
Cu-Ni system. Cu-Ni
system
• Consider 130 0 A
L: 35 wt% Ni
microstuctural a: 46 wt% Ni B
35 46
changes that 32 C 43
accompany the D
24 36 L: 32 wt% Ni
cooling of a a: 43 wt% Ni
C0 = 35 wt% Ni alloy 120 0 E
L: 24 wt% Ni
a: 36 wt% Ni
a
(solid)

110 0
20 30 35 40 50
Adapted from Fig. 9.4, C0 wt% Ni
Callister & Rethwisch 8e.
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•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.

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Development of microstructure in isomorphous alloys
[Fast (non-equilibrium) cooling]

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• 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. 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. ⇒
• Average Ni content of solid grains is higher. 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).

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Cored vs Equilibrium Structures
• Ca changes as we solidify.
• Cu-Ni case: First a to solidify has Ca = 46 wt% Ni.
Last a to solidify has Ca = 35 wt% Ni.
• Slow rate of cooling: • Fast rate of cooling:
Equilibrium structure Cored structure
Uniform Ca:
35 wt% Ni First a to solidify:
46 wt% Ni
Last a to solidify:
< 35 wt% Ni

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Mechanical Properties: Cu-Ni System
• Effect of solid solution strengthening on:
-- Tensile strength (TS) -- Ductility (%EL)
Tensile Strength (MPa)

60

Elongation (%EL)
%EL for pure Cu
400 50 %EL for
TS for pure Ni
pure Ni 40
300
TS for pure Cu 30
200 20
0 20 40 60 80 100 0 20 40 60 80 100
Cu Ni Cu Ni
Composition, wt% Ni Composition, wt% Ni
Adapted from Fig. 9.6(a), Adapted from Fig. 9.6(b),
Callister & Rethwisch 8e. Callister & Rethwisch 8e.

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NiO–MgO phase diagram
35
W. Hume – Rothery rule

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37
 Crystal electroneg r (nm)
Structure
Ni FCC 1.9 0.1246
Au FCC 2.54 0.166 38
Eutectic point and composition (binary mixtures)

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Definitions
• 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.
• Eutectic reaction – transition between liquid and mixture of two solid
phases, α + β at eutectic concentration Ce.
• The melting point of the eutectic alloy is lower than that of the
components (eutectic = easy to melt in Greek) (entropy of mixing).

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41
Binary-Eutectic Systems
has a special composition
2 components with a min. melting T.
Cu-Ag
T(ºC) system
Ex.: Cu-Ag system 1200
• 3 single phase regions L (liquid)
(L, a, b) 1000
• Limited solubility: a L + a 779ºC L+b b
a: mostly Cu TE 800 8.0 71.9 91.2
b: mostly Ag 600
• TE : No liquid below TE ab
• CE : Composition at 400
temperature TE 200
0 20 40 60 CE 80 100
• Eutectic reaction C, wt% Ag
L(CE) a(CaE) + b(CbE) Adapted from Fig. 9.7,
Callister & Rethwisch 8e.
cooling
L(71.9 wt% Ag) a(8.0 wt% Ag)  b(91.2 wt% Ag) 42
heating
EX 1: Pb-Sn Eutectic System
• For a 40 wt% Sn-60 wt% Pb alloy at 150ºC, determine:
-- the phases present Pb-Sn
Answer: a + b T(ºC) system
-- the phase compositions
300
Answer: Ca = 11 wt% Sn L (liquid)
Cb = 99 wt% Sn
-- the relative amount a L+ a
200 183ºC L+b b
of each phase 18.3 61.9 97.8
Answer: 150
S Cb - C0 R S
100
W =
a R+S
=
Cb - Ca a+b
99 - 40 59
= = = 0.67
99 - 11 88 0 11 20 40 60 80 99100
C0 - Ca Ca C0 Cb
Wb = R = C, wt% Sn
R+S Cb - Ca Adapted from Fig. 9.8,
Callister & Rethwisch 8e.
40 - 11 29
= = = 0.33 43
99 - 11 88
EX 2: Pb-Sn Eutectic System
• For a 40 wt% Sn-60 wt% Pb alloy at 220ºC, determine:
-- the phases present: Pb-Sn
Answer: a + L T(ºC) system
-- the phase compositions
300
Answer: Ca = 17 wt% Sn L (liquid)
CL = 46 wt% Sn L+a
-- the relative amount 220
200
a R S L+b b
of each phase 183ºC
Answer:
100
Wa =
CL - C0
=
46 - 40 a+b
CL - Ca 46 - 17
6 0 17 20 40 46 60 80 100
= = 0.21 Ca C0 CL
29 C, wt% Sn
Adapted from Fig. 9.8,
C0 - Ca 23 Callister & Rethwisch 8e.
WL = = = 0.79
CL - Ca 29
44
 L → α + L → α +β
Primary α phase is formed in the α + L region, and the
eutectic structure that includes layers of α and β phases
(called eutectic α and eutectic β phases) is formed upon
45
crossing the eutectic isotherm.
46
Development of Microstructure

L → α +L→ α

In this case of lead-rich alloy (0-2 wt. %

of tin) solidification proceeds in the same
manner as for isomorphous alloys.

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48
At temperatures between the maximum
solid solubility at the eutectic temperature
and room temperature solubility limit, β
phase nucleates as the α solid solubility is
exceeded upon crossing the solvus line.

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L → α +β

No changes above the eutectic temperature TE. At TE

the
liquid transforms to α and β phases (eutectic reaction).

50
Compositions of α and β phases are very different →
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-rich α phase, the 51
light layers are the tin-rich β phase.
How to calculate relative amounts of
microconstituents (primary alpha and
eutectic alpha)?
We = P / (P+Q) (eutectic)
Wα’ = Q / (P+Q) (primary)

How to calculate the total

amounts of phases?

Wα = (Q+R) / (P+Q+R) (α
phase)
Wβ = P / (P+Q+R) (β phase)

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primary α phase

eutectic structure

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 A hypothetical A–B alloy of composition 40 wt% B–60 wt% A at some
temperature is found to consist of mass fractions of 0.66 and 0.34 for the α
and β phases, respectively. If the composition of the α phase is 13 wt% B–87
wt% A, what is the composition of the β phase?

 Draw schematic phase diagrams for binary systems with (a) complete liquid
and solid solubility, (b) complete liquid but zero solid solubility, and (c)
complete liquid and limited solid solubility. (In your sketches label phase fields
and temperatures.)

 A binary alloy having 28 wt % Cu & balance Ag solidifies at 779⁰C. The soild

consists of two pahses α & β. Phase α has 9% Cu whereas phase β has 8% Ag
at 779⁰C. At room temperature these are pure Ag & Cu respectively. Sketch
the phase diagram. Label all fields & lines. Melting points of Cu & Ag are 1083⁰
& 960⁰C respectively. Estimate the amount of α & β in the above alloy at
779⁰C & at room temperature.
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copper–zinc system
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 Eutectoid Transformation

The eutectoid (eutectic-like in Greek) reaction is similar to the eutectic

reaction but occurs from one solid phase to two new solid phases.
Eutectoid Temperature
Eutectoid Isotherm
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 Peritectic
A peritectic reaction - solid phase and
liquid phase will together form a second
solid phase at a particular temperature and
composition upon cooling, e.g. L + α ↔ β

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58
The Iron–Iron Carbide (Fe–Fe3C) Phase Diagram

In their simplest
form, steels are
alloys of Iron (Fe)
and Carbon (C).
The Fe-C phase
diagram consists
of various phases
and regions, but
we
will only consider
the steel part of
the
diagram, up to
around 7%
Carbon.

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• C is an interstitial impurity in Fe. It forms a solid solution with α, γ, δ
phases of iron.
• Maximum solubility in BCC α-ferrite is limited (max. 0.022 wt% at 727
°C) - BCC has relatively small interstitial positions.
• Maximum solubility in FCC austenite is 2.14 wt% at 1147 °C - FCC has
larger interstitial positions.
• Effect of carbon

60
 Types of Iron

• Iron: less than 0.008 wt % C in α−ferrite at room T

• Steels: 0.008 - 2.14 wt % C (usually < 1 wt % ) α-ferrite + Fe3C at
room T
• Cast iron: 2.14 - 6.7 wt % (usually < 4.5 wt %) heavy equipment
casing

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Eutectic: 4.30 wt% C, 1147 Eutectoid: 0.76 wt%C, 727 °C
°C γ(0.76 wt% C) ↔ α (0.022 wt%
L ↔ γ + Fe3C C) + Fe3C 62
When alloy of eutectoid composition (0.76
wt % C) is cooled slowly it forms pearlite,
a lamellar or layered structure of two
phases: α-ferrite and cementite (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.

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In the micrograph, dark areas are
Fe3C layers, light phase is α-ferrite

64
Hypoeutectoid

Compositions to the left of eutectoid (0.022

- 0.76 wt % C) hypoeutectoid (less than
eutectoid -Greek) alloys.

γ → α + γ → α + Fe3C

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• Hypoeutectoid alloys contain proeutectoid ferrite (formed above the
eutectoid temperature) plus the eutectoid pearlite that contain
eutectoid ferrite and cementite.

66
Hypereutectoid

• Compositions to the right of eutectoid

(0.76 - 2.14 wt % C) hypereutectoid
(more than eutectoid -Greek) alloys.
• γ → γ + Fe3C → α + Fe3C

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

68
How to calculate the relative amounts of
proeutectoid phase (α or Fe3C) and pearlite?

69
• Application of the lever rule with tie line that extends from the eutectoid
composition (0.76 wt% C) to α – eutectoid boundary (0.022 wt% C) for
hypoeutectoid alloys and to eutectoid – Fe3C boundary (6.7 wt% C) for
hypereutectoid alloys.

Hypereutectoid alloys:
Fraction of pearlite:
WP = X / (V+X) = (6.7 – C1) / (6.7 – 0.76)
Fraction of proeutectoid cementite:
WFe3C = V / (V+X) = (C1 – 0.76) / (6.7 – 0.76)

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Phases
• α-ferrite - solid solution of C in BCC Fe
Stable form of iron at room temperature. The maximum solubility of C is
0.022 wt%. Transforms to FCC γ-austenite at 912 °C.

• 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.

• 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.

• 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.

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Summary

• Phase diagrams are useful tools to determine:

-- the number and types of phases present,
-- the composition of each phase,
-- and the weight fraction of each phase
given the temperature and composition of the system.
• The microstructure of an alloy depends on
-- its composition, and
-- whether or not cooling rate allows for maintenance of
equilibrium.
• Important phase diagram phase transformations include
eutectic, eutectoid, and peritectic.

72