PHASE DIAGRAMS

• When we combine two elements...

what equilibrium state do we get?

• In particular, if we specify...
--a composition (e.g., wt%Cu - wt%Ag), and
--a temperature (T)

then...
How many phases do we get?
What is the composition of each phase?
How much of each phase do we get?

M. Shim MSE280
 Phase Diagrams
Reading: Callister Ch. 10
• What is a phase?
• What is the equilibrium state when different elements are
mixed?
• What phase diagrams tell us.
• How phases evolve with temperature and composition
(microstructures).

M. Shim MSE280
 PHASES
Phase: A homogeneous portion of a system that has uniform physical
and chemical characteristics.
1. Different physical states: e.g.
vapor, liquid, solid

2. Different chemical composition

syrup, sugar e.g.

M. Shim MSE280
 Equilibrium Phase Diagrams

• Graphic mapping of the

natural tendencies of a
material or a material
system (equilibrium for all
possible conditions).
• Primary variables:
temperature, pressure
and composition.
• P-T diagram (the
simplest).

M. Shim MSE280
 Temperature-Composition
Diagrams
• Engineering
processes conducted
at atmospheric
pressure (P/T
variations).
• The most common:
temperature-
composition phase
diagrams.

M. Shim MSE280
 THE SOLUBILITY LIMIT
• Solubility Limit:
Max concentration for
which only a solution
occurs.

• Ex: Phase Diagram:

Water-Sugar System
Question: What is the
solubility limit at 20C?
65 wt% sugar
Answer: 65wt% sugar.
If Comp < 65wt% sugar: syrup
If Comp > 65wt% sugar: syrup + sugar coexist

• Solubility limit increases with T:

e.g., if T = 100C, solubility limit = 80wt% sugar.

M. Shim MSE280
 COMPONENTS AND PHASES
• Components:
The elements or compounds which are mixed initially
(e.g., Al and Cu, or water and sugar)
• Phases:
The physically and chemically distinct material regions
that result (e.g., α and β, or syrup and sugar)

Aluminum-
Copper
Alloy

Adapted from
Fig. 9.0,
Callister 3e.

M. Shim MSE280
 TEMPERATURE & COMPOSITION (Co)
• Each point on this phase diagram represents equilibrium
• Changing T can change # of phases: path A to B
• Changing Co can change # of phases: path B to C

B
C

A: 2 phases present
(liquid solution ‘n solid sugar)
B: Single phase
C: back to 2 phases
but at different composition
A
Note: this is an equilibrium
phase diagram (What does
it mean to have phase
equilibrium?)
M. Shim MSE280
 Water-Salt Phase Diagram

Solubility limit

Reduction in
freezing point

M. Shim MSE280
 COOLING CURVES
• Cooling curves for NaCl-H20 combinations:

M. Shim MSE280
 Cooling Curves
• Partial equilibrium diagram of NaCl-H20 system

M. Shim MSE280
 SOLUBILITY
• Solubility limits.
• Degree of solubility determines
properties.
• I-Two metals completely soluble in each
other.
• II- Two metals soluble in liquid state and
insoluble in solid state.
• III-Two metals soluble in liquid state and
partially soluble in solid state.
M. Shim MSE280
 COMPLETE SOLUBILITY
• Copper-Nickel equilibrium diagram

M. Shim MSE280
 PARTIAL SOLID SOLUBILITY

• Degree of solubility depends on temperature

• At max. solubility, 183 C: lead holds up to 19.2
wt% tin in a single phase solution, and tin holds
up to 2.5wt% lead and still be a single phase.
M. Shim MSE280
 THREE PHASE REACTIONS

M. Shim MSE280
 PHASE EQUILIBRIUM
Equilibrium: minimum energy state for a given T, P,
and composition (i.e. equilibrium state will persist
indefinitely for a fixed T, P and composition).

Phase Equilibrium: If there is more than 1 phase

present, phase characteristics will stay constant over
time.

Phase diagrams tell us about equilibrium phases as

a function of T, P and composition (here, we’ll always
keep P constant for simplicity).

M. Shim MSE280
 UTILIZATION OF DIAGRAMS
• The phases present.
• Composition of each phase ( single phase
region or two phase region).
• In two phase region a tie-line should be
constructed.
• The amount of each phase present: lever-
law calculation using a tie-line.

M. Shim MSE280
 UNARY SYSTEMS
Single component system
Consider 2 metals:
Cu has melting T = 1085oC
Ni has melting T = 1453oC (at standard P = 1 atm)

T T

liquid

liquid
1453oC

1085oC
solid
solid

Cu Ni
What happens when Cu and Ni are mixed?
M. Shim MSE280
 BINARY ISOMORPHOUS SYSTEMS
2 components Complete liquid and solid solubility

Expect Tm of solution to lie in between Tm of two pure components

T T
For a pure
liquid component,
complete melting
L occurs before T
liquid o
1453 C increases (sharp
phase transition).
But for
1085oC multicomponent
solid systems, there is
S
solid usually a
coexistence of L
0 100 and S.
Cu wt% Ni Ni
M. Shim MSE280
 PHASE DIAGRAMS
• Tell us about phases as function of T, Co, P
• For this course:
--binary systems: just 2 components.
--independent variables: T and Co (P = 1 atm is always used)

• Phase
Diagram for
Cu-Ni system

• Isomorphous
system: i.e.,
complete
solubility of one Adapted from Fig. 9.2(a), Callister 6e.
component in (Fig. 9.2(a) is adapted from Phase
another Diagrams of Binary Nickel Alloys, P.
Nash (Ed.), ASM International,
Materials Park, OH (1991).
Note change in
melting point
M. Shim MSE280
 BINARY ISOMORPHOUS SYSTEMS
What can we learn from
this phase diagram?
1. Phase(s) present.
A: solid (α) only
B: solid and liquid

1. Composition of
those phases
A: 60 wt% Ni
B: 35 wt% Ni overall (how about
in L and S separately?)

Solid-liquid 1. Amount of the

coexistence phases.
region A: 100% α phase
B: % solid and % liquid?

M. Shim MSE280
 PHASE DIAGRAMS: # and types of phases
• Rule 1: If we know T and Co, then we know:
--the # and types of phases present.

• Examples:
A:
1 phase (α)

B:
2 phases (L + α)

Cu-Ni
phase
diagram

M. Shim MSE280
 PHASE DIAGRAMS: composition of phases
• Rule 2: If we know T and Co, then we know:
--the composition of each phase.
Cu-Ni
system
Examples:
• C0 = 35 wt% Ni
• At 1300 C:
– Only liquid (L)
– CL = C0 (= 35 wt% Ni)
• At 1150 C:
– Only solid (α)
– Cα = C0 (= 35 wt% Ni)
• At TB:
– Both α and L
– CL = Cliquidus (= 31,5 wt% Ni)
– Cα = Csolidus (=42,5 wt% Ni)

M. Shim MSE280
 Determining phase composition
in 2-phase region:
1. Draw the tie line.
2. Note where the tie line intersects
the liquidus and solidus lines (i.e.
where the tie line crosses the
phase boundaries).
3. Read off the composition at the
boundaries:
Liquid is composed of CL amount
of Ni (31,5 wt% Ni).
Solid is composed of Cα amount of
Ni (42,5 wt% Ni).

M. Shim MSE280
 PHASE DIAGRAMS: weight fractions of phases
• Rule 3: If we know T and Co, then we know:
--the amount of each phase (given in wt%).
Cu-Ni
• C0 = 35 wt% Ni system
• At 1300 C:
– Only liquid (L)
– WL = 100 wt%, Wα = 0 wt%
• At 1150 C:
– Only solid (α)
– WL = 0 wt%, Wα = 100 wt%
• At TB:
– Both α and L
– WL = S/(R+S) =
(42,5-35)/(42,5-31,5) = 68 wt%
– Wα = R/(R+S) =
(35-31,5)/(42,5-31,5) = 32 wt%
The lever rule
M. Shim MSE280
 LEVER RULE
Determining phase amount in the
2-phase region:
1. Draw the tie line.
2. Determine the “distance from the
point of interest (B) to each of
the phase boundaries.
R = Co – CL
S = Cα - Co

3. Mass fractions (wt%) of each

phase:
S Cα − Co 4 .52 − 3 5
Liquid: W = = = = 0.6
R + S Cα − C L 4 .52 − 3 .51
L

R C − CL 3 −5 3 .51
Solid: Wα = = o = = 0.3
R + S Cα − C L 4 .52 − 3 .51
i.e. 68% of the mass is liquid and 32% of the mass is solid.
M. Shim MSE280
 LEVER RULE: Derivation
Since we have only 2 phases:

WL + Wα = 1 (1)

Conservation of mass requires that:

Amount of Ni in α-phase + amount of Ni in liquid phase = total amount of Ni
or
Wα Cα + WL C L = Co (2)

From 1st condition, we have: Wα = 1 − WL

Sub-in to (2): (1 − WL )Cα + WL C L = Co

Solving for WL and Wα gives :

Cα − Co Co − C L
WL = Wα =
Cα − C L Cα − C L
M. Shim MSE280
 LEVER RULE: Derivation
• A geometric interpretation:

moment equilibrium:
WLR = WαS

1− Wα
solving gives Lever Rule

• Combine above equations:

M. Shim MSE280
 We can also express in terms of volume fractions:

v _o o l_ fα vα
Vα = =
t o _ tv a o lvαl + vL
m _ o _ ac f os _ jsm W j × t op_ m
Since ρj = =
v _ o o_ j f l vj

WjMto ta
νj = substitute this relation (for each component) into
ρj volume fraction definition – Mtotal cancels out.

Wα / ρα WL / ρ L
Vα = VL =
Wα / ρα + WL / ρ L Wα / ρα + WL / ρ L

M. Shim MSE280
 MICROSTRUCTURES in isomorphous alloys
Microstructures will vary on the cooling rate (i.e. processing conditions)

1. Equilibrium Cooling: Very slow cooling to allow phase equilibrium to

be maintained during the cooling process.
a (T>1260oC): start as
homogeneous liquid solution.
b (T ~ 1260oC): liquidus line
reached. α phase begins to
nucleate. Cα = 46 wt% Ni; CL = 35 wt% Ni
c (T= 1250oC): calculate composition
and mass fraction of each phase.
d (T~ 1220oC): solidus line reached.
Nearly complete solidification.
Cα = 35 wt% Ni; CL = 24 wt% Ni

e (T<1220oC): homogeneous solid

solution with 35 wt% Ni.

M. Shim MSE280
 Example problem

• 65 wt% Ni – 35 wt% Cu alloy is heated

to T within the α+L region. If α-phase
contains 70 wt% Ni, determine:
a. Temperature of the alloy.
b. Composition of the liquid phase.
c. Mass fraction of both phases.

M. Shim MSE280
 Non-equilibrium cooling
Fast cooling, but how fast?
Fast w.r.t. diffusion

Since diffusion rate is especially low in solids, consider case where:

Cooling rate >> diffusion rate in solid

Cooling rate << diffusion rate in liquid
(equilibrium maintained in liquids phase)

M. Shim MSE280
 NON-EQUILIBRIUM cooling
a’ (T>1260oC): start as
homogeneous liquid solution.
b’ (T ~ 1260oC): liquidus line
reached. α phase begins to nucleate.
Cα = 46 wt% Ni; CL = 35 wt% Ni
c’ (T= 1250oC): solids that formed at pt b’
remain with same composition (46wt%) and
new solids with 42 wt% Ni form around the
existing solids (Why around them?).
d’ (T~ 1220oC): solidus line reached. Nearly
complete solidification.
•Previously solidified regions maintain original
composition and further solidification occurs at 35
wt% Ni.

e (T<1220oC): Non-equilibrium solidification

complete (with phase segregation).

M. Shim MSE280
 CORED VS EQUILIBRIUM PHASES
• Cα changes as we solidify.
• Cu-Ni case: First α to solidify has Cα = 46wt%Ni.
Last α to solidify has Cα = 35wt%Ni.
• Fast rate of cooling: • Slow rate of cooling:
Cored structure Equilibrium structure

M. Shim MSE280
 MECHANICAL PROPERTIES: Cu-Ni System

• Effect of solid solution strengthening on:

--Tensile strength (TS) --Ductility (%EL,%AR)

Adapted from Fig. 9.5(a), Callister 6e. Adapted from Fig. 9.5(b), Callister 6e.

M. Shim MSE280
 Mechanical Properties of Copper-
Nickel and Copper-Zinc Alloys
Figure 4.6 Mechanical
properties of copper-nickel
and copper-zinc alloys as a
function of their
composition. The curves
for zinc are short, because
zinc has a maximum solid
solubility of 40% in
copper. Source: L. H. Van
Vlack; Materials for
Engineering. Addison-
Wesley Publishing Co.,
Inc., 1982.

M. Shim MSE280
 BINARY-EUTECTIC SYSTEMS
has a special composition
2 components with a min. melting T.
Cu-Ag
Ex.: Cu-Ag system
system
• 3 single phase regions
(L, α, β)
• Limited solubility:
α : FCC, mostly Cu
β : FCC, mostly Ag
• T E : No liquid below TE
• CE : Min. melting T
composition
• 3 two phase regions
• Cooling along dotted
Adapted from Fig. 9.6,
line: Callister 6e. (Fig. 9.6 adapted
from Binary Phase Diagrams, 2nd ed., Vol. 1, T.B.
L (71.9%)  α (8%) + β (91.2%) Massalski (Editor-in-Chief), ASM International,
Materials Park, OH, 1990.)
M. Shim MSE280
 EUTECTIC POINT
Eutectic point: Where 2 liquidus lines
meet (pt. E).
Sometimes also referred to as invariant
point.

Eutectic Reaction:
cool
L(CE) α(CαE) + β(CβE)
heat
similar to one component (pure) system
except 2 solid phases.

Eutectic Isotherm: Horizontal solidus

Cu-Ag phase diagram line at T = TE.

M. Shim MSE280
 EUTECTIC SYSTEM: Example
At 150oC for a 40wt% Sn/ 60
wt% Pb alloy:
1. What phases are present?
2. What are the compositions of
the phases present?
3. What are the mass fractions of
the phases?
4. What are the volume
fractions?
For a 10wt% Sn/ 90wt% Pb alloy:
1. At what T, can a state with 50%
liquid be achieved?
2. At 250oC, how much Sn must
Pb-Sn phase diagram
be added to achieve the same
state (50% liquid)?
M. Shim MSE280
 Exp: Pb-Sn eutectic system (1)
• For a 40wt%Sn-60wt%Pb alloy at 150C, find...
Pb-Sn
system
--the phases present

--the compositions of
the phases

--the relative amounts

of each phase

Adapted from Fig. 9.7,

Callister 6e. (Fig. 9.7 adapted
from Binary Phase Diagrams, 2nd ed., Vol. 3, T.B.
Massalski (Editor-in-Chief), ASM International,
Materials Park, OH, 1990.)
M. Shim MSE280
 Exp: Pb-Sn eutectic system (2)
• For a 40wt%Sn-60wt%Pb alloy at 150C, find...
--the phases present: Pb-Sn
α+β system
--the compositions of
the phases:
Cα = 11wt%Sn
Cβ = 99wt%Sn
--the relative amounts
of each phase:
(lever rule)

Adapted from Fig. 9.7,

Callister 6e. (Fig. 9.7 adapted
from Binary Phase Diagrams, 2nd ed., Vol. 3, T.B.
Massalski (Editor-in-Chief), ASM International,
Materials Park, OH, 1990.)
M. Shim MSE280
 MICROSTRUCTURES in Eutectic Alloys

1. One component rich composition.

a: start with homogeneous liquid.
b: α-phase solids with liquid.
Compositions and mass fractions can be
found via tie lines and lever rule.
c: α-phase solid solution only.

Net result: polycrystalline α solid.

Cooling at this composition is similar to

binary isomorphous systems.

Partial Pb-Sn phase diagram

M. Shim MSE280
 MICROSTRUCTURES in Eutectic Alloys

2. One-component rich but cooling to α + β

coexistence.
d: homogeneous liquid.
e: α + L phase (same as previous but at
different compositions and mass fractions).
f: all α-phase solid solution.
g: α + β phase (passing through solvus line
leads to exceeding solubility limit and β phase
precipitates out).

Net result: polycrystalline α-solid with fine β

crystals.

M. Shim MSE280
 MICROSTRUCTURES in Eutectic Alloys

3. Cooling through eutectic point.

h: homogeneous liquid.
i: solidification via eutectic reaction
cool
L(CE) α(CαE) + β(CβE)
heat

note: α and β phases have very

different compositions than the Eutectic Structure: layered (lamellar)
original composition of the liquid (e.g. structure.
Cα = 18.3 wt% Sn; Cβ = 97.8 wt% Sn Why does this structure form?
whereas CL = 61.9 wt% Sn).

M. Shim MSE280
 EUTECTIC STRUCTURE
Pb-Sn Eutectic microstructure

Sn
In order to achieve large
α Pb rich
homogeneous regions, long
L diffusion lengths are required.
β Sn rich
Pb

Lamellar structure forms because

relatively short diffusion lengths
are required.

M. Shim MSE280
 MICROSTRUCTURES in Eutectic Alloys
Hypoeutectic 4. Cooling through eutectic
isotherm.
j: homogeneous liquid.
k: α + L phases: use tie lines
and lever rule.
l: just above eutectic isotherm
compositions given but what
about mass fraction?
m: remaining liquid transforms
to eutectic structure upon
crossing eutectic isotherm.
Microconstituent: an element
of a microstructure with
identifiable and characteristic
structure (at pt. m there are 2
microconstituents: primary α
and eutectic structures)
M. Shim MSE280
 MICROSTRUCTURES in Eutectic Alloys
• 18.3wt%Sn < Co < 61.9wt%Sn
• Result: α crystals and a eutectic microstructure

Pb-Sn
system

Adapted from Fig. 9.14,

Callister 6e.

M. Shim MSE280
 Just above the eutectic isotherm
at C4’:
P
WL = All of this
P+Q amount will
turn into
eutectic
structure (We).

Primary α structure: Total α (primary + eutectic): Total β (all in eutectic):

Wα ' =
Q Q+R P
Wα = Wβ =
P+Q P+Q+ R P+Q+ R
Note: this is for equilibrium cooling. Non-equilibrium cooling will lead to:
Cored primary phases
Increased fraction of eutectic microconstituent
M. Shim MSE280
 HYPOEUTECTIC & HYPEREUTECTIC

Adapted from Fig. 9.7,

Callister 6e. (Fig. 9.7
adapted from Binary
Phase Diagrams, 2nd
ed., Vol. 3, T.B. Massalski
(Editor-in-Chief), ASM
International, Materials
Park, OH, 1990.)

(Figs. 9.12 and

9.15 from Metals
Handbook, 9th ed.,
Vol. 9,
Metallography and
Microstructures,
American Society
for Metals,
Materials Park,
OH, 1985.)

Adapted from Adapted from Fig. 9.15,

Fig. 9.15, Callister 6e. Adapted from Fig. 9.12, Callister 6e. (Illustration
Callister 6e. only)
M. Shim MSE280
 COMPLEX PHASE DIAGRAMS
Intermediate phases
Intermediate solid solutions (intermediate phases): Solid solutions that do not
extend to pure components in the phase diagram.
Cu-Zn

Terminal solutions: α
and η.

Intermediate solutions:
β, γ, δ and ε.

Tie lines and lever rule can

be used to determine
compositions and wt% of
phases.
e.g. at 800oC with 70 wt%
Zn
CL = 78 wt% Zn
Cγ = 67 wt% Zn

M. Shim MSE280
 EUTECTOID and PERITECTIC reactions

Eutectoid reaction: one solid phase turning into two other solid phases upon cooling
cool
e.g. δ γ+ε
heat
Peritectic reaction: one solid phase transforms into liquid and a different solid
phases upon heating cool
e.g. δ + L ε
M. Shim heat MSE280
 Congruent phase transformation
Congruent transformation: no change in composition upon phase
transformation.
Incongruent transformation: phase transformation where at least one of the
phases go through composition change.

At what overall
composition does Mg2Pb
melt congruently?

M. Shim MSE280
 INTERMETALLIC COMPOUNDS
Intermediate (intermetallic) compounds: discrete metal compounds rather
than solutions (i.e. distinct chemical formula).
AxBy: in solution x and y can vary
in compounds x and y are fixed (always fixed composition of A and B).
Mg-Pb phase diagram

Can be considered as two

phase diagrams put
together back to back.

Mg-Mg2Pb phase diagram Mg2Pb-Pb phase diagram

M. Shim MSE280
 INTERMETALLIC COMPOUNDS: Example

A 50wt% Pb/50wt% Mg
alloy is heated to
300oC. The mass
fraction of each phase
is 0.5.
1. What are the phases
present?
2. What are the
compositions of the
phases?

M. Shim MSE280
 CERAMIC PHASE DIAGRAMS
Al2O3-Cr2O3 MgO-Al2O3

M. Shim MSE280
 GIBBS PHASE RULE
Number of non-
Number of compositional variables
phases present P+F=C+N (Temperature & Pressure)

Degree of freedom (externally controllable Number of

parameters: i.e. T, P, and C) components

e.g. Cu-Ag phase diagram

Cu and Ag are the only components

-> C = 2

Temperature is the only non-compositional variable

here (i.e. fixed pressure).
-> N = 1 (but in general N = 2)

When 2 phases are present

-> P = 2 which leads to F = C+N-P = 2+1-2 = 1

When only 1 phase is present.

-> P = 1 which leads to F = 2

What does this mean? Why should you care?

M. Shim MSE280
 GIBBS PHASE RULE
In the previous example of Cu-Ag phase diagram, when F = 1, only one
parameter (T or C) needs to be specified to completely define the system.

e.g. (for α+L region)

If T is specified to be 1000oC,
compositions are already determined
(Cα and CL).

Or

If composition of the a phase is

specified to be Cα then both T and CL
are already determined.

Cα CL
M. Shim MSE280
 GIBBS PHASE RULE
When F = 2, both T and C have to be specified to completely define the
state of the system.

e.g.(for α region)
If T is specified to be 800oC, Cα can be
any where between 0 to ~8 wt% Ag)

Or

If composition of the a phase is

specified to be Cα = 3 wt%, then T and
can be any where between ~600 to
1100oC.

Cα

M. Shim MSE280
 GIBBS PHASE RULE
Where in the Cu—Ag diagram, is there a 0 degree of freedom?
(i.e. T, P, and C are all fixed)

M. Shim MSE280
 IRON-CARBON SYSTEM
Typical metal (e.g. Cu) Iron
T(oC)
T

Liquid
Liquid
1538
Ferrite (BCC)
Tm 1394

Austenite (FCC)
Solid 912
Ferrite (BCC)

M. Shim MSE280
 IRON-CARBON SYSTEM
Eutectic point

Eutectoid

Note: only goes out to 6.7

wt% C (100 wt% Fe3C
intermediate compound)

FCC γ-phase has highest C concentration (2.14 wt% C) whereas BCC α-phase has low
solubility (0.022 wt% C). Recall FCC is close packed (i.e. larger APF). Why is C more soluble
in FCC?
M. Shim MSE280
 IRON-CARBON (Fe-C) PHASE DIAGRAM

• Pure iron: 3 solid

phases
– BCC ferrite (α)
– FCC Austenite (γ)
– BCC δ
• Beyond 6.7% C
cementite (Fe3C)
• Eutectic: 4.3% C
– L  γ + Fe3C
– (L  solid + solid)
• Eutectoid: 0.76% C
– γ  α + Fe3C
– (solid  solid +
solid)

M. Shim MSE280
 Iron-Carbon Equilibrium Diagram
• δ − f e r r ,(present
it only at extreme temperatures)
• Austenite, (FCC, high formability, high solubility of C,
over 2%C can be dissolved in it, most of heat
treatments begin with this single phase).
• Ferrite, BCC, stable form of iron below 912 deg.C,
only up to 0.02 wt% C in solid solution and leads to
two phase mixture in most of steels.
• Cementite (iron-carbide), stoichiometric intermetalic
compound, hard, brittle, exact melting point
unknown.
• Currie point (770 deg. C), atomic level nonmagnetic-
to-magnetic transition.
M. Shim MSE280
 Austenite, Ferrite, and
Martensite

Figure 4.9 The unit cells for (a) austenite, (b) ferrite, and (c) martensite. The effect of percentage of
carbon (by weight) on the lattice dimensions for martensite is shown in (d). Note the interstitial
position of the carbon atoms (see Fig. 1.9). Note, also, the increase in dimension c with increasing
carbon content; this effect causes the unit cell of martensite to be in the shape of a rectangular prism.

M. Shim MSE280
 THREE PHASE REACTIONS
• Peritectic, at 1495 deg.C, with low wt% C
alloys (almost no engineering importance).
• Eutectic, at 1148 deg.C, with 4.3wt% C,
hapends to all alloys of more than
2.11wt% C and they are called cast irons.
• Eutectoid, at 727 deg.C with eutectoid
composition of 0.77wt% C, alloys bellow
2.11%C miss the eutectic reaction to
create two-phase mixture. They are steels.
M. Shim MSE280
 INVARIANT REACTIONS IN FE-C SYSTEM
A horizontal line always indicates an invariant reaction
in binary phase diagrams
Peritectic Reaction

α (0.1 w % C ) + L (t 0.5 w % C ) t → δ (09 .1 w3 % C8)

o
1 C 4

Eutectic Reaction

L (4.3 w % C ) t→ γ (25.1 w % C ) + F 3tC (6.6 w

o
C 1 1 0
e % C7)

Eutectoid Reaction

γ (0.8 w % C ) 
tC →2 α (0.50 w % C2) + F 3tC (6.6 we % C7)
o
7

M. Shim MSE280
 Mild steel
THE IRON-CARBON SYSTEM 0-0.3 wt% C

Bicycle frame
Ship hull
Car body
1410

1150
Medium C steel
0.4-0.7 wt% C

steel
910 Cast iron Rail wheel
rail axle
725 rails
0.8
0.02 High C steel
0.8-1.4 wt% C
Razor blades
scissors, knives
M. Shim MSE280
 STEELS

A u
0.7 % C ; F7 →
s CF t ee
C0.0 % C ; B2 +nC
rC rCi et i
6.6 % C

M. Shim MSE280
 EUTECTOID COOLING

cool
γ (0.76 wt% C) α (0.022 wt% C)
heat + Fe3C (6.7 wt% C)

Pearlite structure

Layered structure forms due to the same reason as eutectic structure formation.
M. Shim MSE280
 EUTECTOID POINT: LEVER RULE
• Just below the
eutectoid point:

• Wα = (6.7-0.76)/(6.7-
0.022) = 89%

• WFe3C = (0.76-
0.022)/(6.7-0.022) =
11%

M. Shim MSE280
 HYPOEUTECTOID ALLOYS
Cooling below eutectoid
composition.
c: homogeneous γ solid.

d: α + γ coexistence. α-phase
nucleate at the grain boundaries
(Why?).

e -> f:
- crossing eutectoid isotherm will
cause all remaining γ-phase into
eutectoid structure.
- α-phase that formed prior to
eutectoid isotherm are called
proeutectoid ferrite.
C − 0.0 2
Fraction of pearlite = W p = o
0.7 −
6 0.0 2

Fraction of proeutectoid α = Wα ' = 0.7 −6 Co

0.7 −
6 0.0 2
M. Shim MSE280
 HYPEREUTECTOID ALLOYS
Cooling above the
eutectoid composition
Compositions and wt% can be
found similarly as hypoeutectoid
cooling.

Instead of proeutectoid α,
proeutectoid cementite appears.

M. Shim MSE280
 Eutectoid Hypoutectoid Hypereutectoid
steel steel steel
α+Fe3C α+Fe3C α+Fe3C
Pearlite Pearlite + Pearlite +
proeutectoid ferrite proeutectoid
cementite

M. Shim MSE280
 Example problem

For 0.35 wt% C, at T just below

eutectoid isotherm,
determine:
a) Fractions of total ferrite and
cementite phases.
b) Fractions of proeutectoid
ferrite and pearlite.
c) Fraction of eutectoid ferrite.

M. Shim MSE280
 Influence of other alloying elements

Changes eutectoid T

Changes eutectoid composition

Useful processing info to control microstructure.

M. Shim MSE280
 CAST IRONS
• Iron-Carbon alloys of
2.11%C or more are
cast irons.
• Typical composition:
2.0-4.0%C,0.5-3.0% Si,
less than 1.0% Mn and
less than 0.2% S.
• Si-substitutes partially
for C and promotes
formation of graphite as
the carbon rich
component instead
Fe3C.
M. Shim MSE280
 GRAY CAST IRON
• Composes of: 2.5-4.0%C,
1.0-3.0%Si and 0.4-1.0%
Mn.
• Microstructure: 3-D graphite
flakes formed during eutectic
reaction. They have pointed
edges to act as voids and
crack initiation sites.
• Sold by class (class 20 has
min. tensile strength of
20,000 psi is a high C-
equivalent metal in ferrite
matrix ). Class 40 would
have pearlite matrix.
M. Shim MSE280
 GRAY CAST IRON
• Properties: excellent compressive
strength, excellent machinability, good
resistance to adhesive wear (self
lubrication due to graphite flakes),
outstanding damping capacity ( graphite
flakes absorb transmitted energy), good
corrosion resistance and it has good
fluidity needed for casting operations.
• It is widely used, especially for large
equipment parts subjected to
compressive loads and vibrations.
M. Shim MSE280
 WHITE CAST IRON
• Composes of: 1.8-3.6%C, 0.5-1.9%Si and
0.25-0.8%Mn.
• All of its carbon is in the form of iron-
carbide (Fe3C). It is called white because
of distinctive white fracture surface.
• It is very hard and brittle (a lot of Fe3C).
• It is used where a high wear resistance is
dominant requirement (coupled hard
martensite matrix and iron-carbide). Thin
coatings over steel (mill rolls).
M. Shim MSE280
 MALLEABLE CAST IRON
• Formed by extensive heat
treatment around 900 degC,
Fe3C will dissociate and form
irregular shaped graphite
nodules. Rapid cooling
restricts production amount
to up to 5 kg. Less voids and
notches.
• Ferritic MCI: 10% EL,35 ksi
yield strength, 50 ksi tensile
strength. Excellent impact
strength, good corrosion
resistance and good
machinability.
M. Shim MSE280
 PEARLITIC MALLEABLE CAST IRON

• Pearlitic MCI: by rapid cooling through

eutectic transformation of austenite to
pearlite or martensite matrix.
• Composition: 1-4% EL, 45-85 ksi yield
strength, 65-105 ksi tensile strength.
Not as machinable as ferritic
malleable cast iron.

M. Shim MSE280
 DUCTILE CAST IRON

• Without a heat treatment by addition of

ferrosilicon (MgFeSi) formation of smooth
spheres (nodules) of graphite is promoted.
• Properties: 2-18% EL, 40-90 ksi yield
strength, 60-120 ksi tensile strength.
• Attractive engineering material due to:
good ductility, high strength, toughness,
wear resistance, machinability and low
melting point castability.
M. Shim MSE280
 MALLEABLE CAST IRON
• Ductile iron with
ferrite matrix (top)
and pearlite matrix
(bottom) at 500X.

• Spheroidal shape
of the graphite
nodule is achieved
in each case.
M. Shim MSE280
 MICROSTRUCTURE

• Globular cast iron

M. Shim MSE280
 Microstructures for Cast Irons
(a) (b) (c)

Figure 4.13 Microstructure for cast irons. Magnification: 100X. (a) Ferritic gray iron with graphite
flakes. (b) Ferritic Ductile iron (nodular iron), with graphite in nodular form. (c) Ferritic malleable
iron; this cast iron solidified as white cast iron, with the carbon present as cementite, and was
heat treated to graphitize the carbon. Source: ASM International.

M. Shim MSE280
 CONCEPTS TO REMEMBER
• Phases, chemical composition, phase equilibrium.
• Phase diagrams tell us about:
– Number and types of phases present.
– Composition of each phase.
– Mass fraction (wt%) of each phase.
• Binary isomorphous systems.
• Binary eutectic systems.
• Microstructure evolution in cooling (equilibrium vs. non-
equilibrium).
• Eutectic, eutectoid, and peritectic reactions.
• Hyper- and hypoeutectic & hyper- and hypoeutectoid
alloys
• Fe-C phase diagram.
• Phase diagrams help us to determine the equilibrium
microstructures which in turn determines the
properties of materials!
M. Shim MSE280