Chapter-4 Phase Diagrams

o Phase diagrams are maps that give the relationships

between phases in equilibrium in a system as a function of
temperature, pressure and composition. The study of phase
relationships play an important role in the understanding of
properties of materials.

o Knowledge and understanding of phase diagrams is

important to the engineer relates to the design and control
of heat-treating procedures; properties of materials are
functions of their microstructures, and, consequently, of
their thermal histories.

o The phases as determined from the microstructure of the

material may not be an equilibrium phase (due to some
heat treatment), still the phase diagrams provides the first
step to get an insight into microstructure control 1
o Components:
The term component is frequently used in this discussion; components
are pure metals and/or compounds of which an alloy is composed. For
example, in a copper–zinc brass, the components are Cu and Zn. The
elements or compounds that are mixed initially; Al-Cu alloy (Al and Cu).

o Phases:
A phase is a homogenous, physically distinct and mechanically
separable portion of the material with a given chemical composition and
structure.
 (lighter
Aluminum-
phase)
Copper
Alloy
(darker
phase)

2
Equilibrium
o A system is at equilibrium if its free energy is at a minimum, given a
specified combination of temperature, pressure and composition.
o The (macroscopic) characteristics of the system do not change with
time — the system is stable.
o A change in T, P or C for the system will result in an increase in the
free energy and possible changes to another state whereby the free
energy is lowered.
o Phase diagrams are mostly equilibrium phase diagrams that show
the transformation from one phase to another with change in
temperature or composition
o Equilibrium is defined in terms of chemical potential of particular
component in a phase. Mathematically, it is given as:

A is the element, α, β, γ are the phases. It states that for an equilibrium to

exist, the chemical potential of component A in phase α is equal to chemical
potential of component A in phase β and component A in phase γ 3
Gibbs Phase Rule
Gibbs phase rule is a criterion that determines how many phases can coexist
within a system at equilibrium
o For any system, say P number of phases are in equilibrium. Each phase
has say C number of components
o Number of variables required to specify completely the composition of a
particular phase is “(C-1)”. Thus, for P phases, number of variables required
to specify the system is P(C-1)
o Phase equilibrium is usually specified at particular temperature T and
pressure P. Thus T and P adds to two external variables and the total
number of variables become P(C-1)+2
o For each component, we need to define chemical potential of just one
phase and all other phases get automatically defined. Thus, out of total
C(P-1) variables are fixed

Therefore, number of independent variables required to define the system are

P(C-1) +2 - C(P-1)
o Number of independent variables gives the degree of freedom F for the
system. Therefore, we can write as:

o In order to simplify the representation of phase diagrams on paper, these

are usually drawn at constant atmospheric pressure. Thus, pressure is
kept constant and number of external variables reduces to 1. The phase
rule can then be written as below and is known as condensed phase rule
 Phase Equilibria: Solubility Limit
o For many alloy systems and at some specific temperature,
there is a maximum concentration of solute atoms that may
dissolve in the solvent to form a solid solution; this is called
a solubility limit
o The addition of solute in
Sugar/Water Phase Diagram
excess of this solubility limit
100
results in the formation of Solubility
compound that has a distinctly Limit L

Temperature (°C)
80
different composition. (liquid)
60 L +
Question: What is the (liquid solution S
40
solubility limit for sugar i.e., syrup) (solid
in water at 20°C? 20 sugar)

Answer: 65 wt% sugar.

0 20 40 6065 80 100
At 20°C, if C < 65 wt% sugar: syrup
Water

C = Composition (wt% sugar)

Sugar
At 20°C, if C > 65 wt% sugar: syrup +
sugar
One Component Phase Diagram
o Perhaps the simplest and
easiest type of phase
diagram to understand is
that for a one-component
system, in which
composition is held
constant (i.e., the phase
diagram is for a pure
substance);

o Pressure and temperature are the variables. This one-component phase

diagram (or unary phase diagram) [sometimes also called a pressure–
temperature (or P–T) diagram] is represented as a two dimensional plot
of pressure (ordinate, or vertical axis) versus temperature (abscissa, or
horizontal axis).
7
 Gibbs Free Energy
Gibbs free energy, G (J/mol): measure of relative stability
of a phase at constant temperature and pressure

G = E + PV  TS
Intensive variables : Temperature, T (K); Pressure, P (Pa);
Extensive variables : Internal energy E (J/mol); Volume, V (m3),
Entropy (J/K mol)
Differentiating the free energy equation,
 Solid stable Liquid stable

G

Solid (GS)

G → ve
G →

Liquid (GL)
T
G → +ve
Tm T →
Since, driving force along the phase change process is same

P G1 P, T   G2 P, T 
phase
boundary
Slope of the curve

T T

Since S1 - S2 = L/T (L is the latent heat), we arrive at

the following relation:

This is known as Clausius-Clapeyron Relation

 Phase Diagram of H2O

dT T Vliq  Vsol 
 0
dP L

o For most “normal” substances, the slope of the melting curve is positive
(VL>VS). The phase diagram for water shows the characteristic negative
slope of the solid-liquid equilibrium curve. The ice is less dense than
water (VL<VS): As ice melts into water the change in entropy (or the
latent heat) is positive, while the change in volume is negative, hence
the negative slope.
Binary Phase Diagrams
o Indicate phases as a function of Temp, Comp and Pressure.

o Focus on:
 Binary systems: 2 components.
 Independent variables: T and C (P = 1 atm is almost always used).

We will primarily deal with

o Isomorphous System- Both components have complete

solubility in each other in liquid as well as solid state

o Eutectic System: Have complete solubility in liquid state

but limited solubility or complete insolubility in the solid
state
12
Isomorphous Vs Eutectic System
o Mixtures of some metals, such as copper & nickel, are completely
soluble in both liquid and solid states for all concentrations of both
metals.
o Copper & nickel have the same crystal structure (FCC) and have
nearly the same atomic radii. The solid formed by cooling can
have any proportion of copper & nickel. Such completely miscible
mixtures of metals are called Isomorphous.

o By contrast, a mixture of lead & tin that is eutectic is only partially

soluble when in the solid state. Lead & tin have different crystal
structures (FCC versus BCT) and lead atoms are much larger.
o No more than 18.3 weight % solid tin can dissolve in solid lead and
no more than 2.2 weight % of solid lead can dissolve in solid tin
o The solid lead-tin alloy consists of a mixture of two solid phases,
one consisting of a maximum of 18.3 wt% tin (the alpha phase)
and one consisting of a maximum of 2.2 wt% lead (the beta
phase).
13
Isomorphous Phase Diagrams
Cu-Ni system: T(°C)
1600
o The liquid L is a homogeneous
liquid solution composed of Cu 1500 L (liquid)
and Ni.
o The α phase is a substitutional 1400
solid solution consisting of Cu
and Ni atoms with an FCC crystal 1300
structure.
1200 
o At temperatures below 1080 C,
(FCC solid
Cu and Ni are mutually soluble in 1100
each other in the solid state for solution)
all compositions. 1000
0 20 40 60 80 100
Wt.% Ni

oThe complete solubility is explained by their FCC structure, nearly

identical atomic radii and electro-negativities, and similar valences.
oThe Cu-Ni system is termed Isomorphous because of this complete
liquid and solid solubility of the 2 components. 14
 Criteria for Solid Solubility
Simple system (e.g., Ni-Cu solution)

Crystal
Electronegativity r (nm)
Structure
Ni FCC 1.9 0.1246

Cu FCC 1.8 0.1278

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

similar Electronegativities and atomic radii (W. Hume –
Rothery rules) suggesting high mutual solubility.

o Ni and Cu are totally soluble in one another for all proportions.

15
Binary Phase Diagram and Gibbs Free Energy
Net free energy for mixing of two components as function of
composition and any temperature T

GαA

GαB

Gα

0 XB 1
o Let’s construct a binary phase
diagram for the simplest case:
G solid
B

o A and B components are mutually

soluble in any amounts in both G solid T1
A
solid (isomorphous system) and G liquid
B
liquid phases, and form ideal G liquid
solutions (completely miscible
A G solid
system)

o We have 2 phases – liquid and G liquid

solid. Let’s consider Gibbs free
energy curve for these phases 0 XB 1
at different temperatures

T1 is above the equilibrium melting temperatures of both pure

components i.e. T1>Tm(A)>Tm(B); Liquid phase is more stable for
any composition
The temperature is now decreased to say T2 such that
T2=Tm(A) and >Tm(B);

solid
G B

T2 G liquid
B
G Aliquid = G Asolid
G solid

G liquid

0 XB 1
Liquid phase is still the more stable
phase on the B composition side
With further reduction in temperature to T3 such that T3<T2 but >
Tm(B) the liquid and solid curves will cross each other

T3 G solid
B
liquid
G A

G solid
solid
G A liquid
G B

G liquid

solid solid +
liquid liquid

X1 X2
0 XB 1
Finally, we reach at temperature T4 such that T4 =Tm(B)

T4
liquid
G A
liquid
G liquid solid
G B =G B

G Asolid

G solid

0 XB 1
At T4 and below this temperature the Gibbs free energy of the
solid phase is lower than the G of the liquid phase in the whole
range of compositions – the solid phase is the only stable phase.
Based on the Gibbs free energy curves we can now construct a
phase diagram for a binary isomorphous systems
solid
G liquid G B
T1
A
T3
G solid
G solid
A G liquid
s B
G liquid
l
solid solid +
liquid liquid
s
T2
T T1
l
T2

l T4 T3
T4
s
T5
0 XB 1
Determination of Phases Present
o Rule 1: If we know T and Co, then we know:
--how many phases and which phases are present.
T(°C)
1600
Examples:
1500 L (liquid)
s
A(1100, 60): u

B(1250,35)
id
1 phase:  1400 il qu us Cu-Ni
olid
s phase
B(1250, 35): 1300 +  
diagram
2 phases: L +  L (FCC solid
1200 solution)
Melting points: Cu = 1100 A(1100,60)
1085°C, Ni = 1453 °C
1000
0 20 40 60 80 100 wt% Ni
Solidus - Temperature where alloy is completely solid. Above this line, liquefaction
begins.
Liquidus - Temperature where alloy is completely liquid. Below this line, solidification
begins.
 Composition of Phases
o Rule 2: If we know T and Co, then we know:
--the composition of each phase.
Cu-Ni
o Examples: T(°C)
system
For 35 wt.% Ni TA A
tie line dus
i
1300 L (liquid) liqu
At TA = 1320°C: 
L +
Only Liquid (L) present B
sol
id
s u
CL = C0( = 35 wt% Ni) T B

At TD = 1190°C: L + (solid)
1200 D
Only Solid (a) present TD
C = C0( = 35 wt% Ni) 20 3032 35 4043 50
At TB = 1250°C: CLCo C wt% Ni
Both  and L present
CL = C liquidus ( = 32 wt% Ni)
C = Csolidus ( = 43 wt% Ni)
23
The Lever Rule
o Tie line – connects the phases in equilibrium with each
other – also sometimes called an isotherm
T(ºC)
tie line
What fraction of each phase?
1300 L (liquid)
Think of the tie line as a lever
B
TB ML M

1200 (solid)
R S

20 30CL
C0 40 C 50 R S
wt% Ni M x S  ML x R
ML S C  C0 R C  CL
WL     W   0
M L  M  R  S C   CL R  S C   CL
24
The Lever Rule
• Sum of weight fractions: WL  W  1
• Conservation of mass (Ni): Co  WL CL  WC
• Combine above equations:
 C  Co  S Co  CL  R
WL W 
C  CL R S  C  CL R  S

• A geometric interpretation:
Co moment equilibrium:
CL C
WLR  WS
R S

WL W 1 W
solving gives Lever Rule
9
Weight Fraction of Phases
o Rule 3: If we know T and Co, then we know:
--the amount of each phase (given in wt%).
o Examples:
Co = 35wt%Ni T(°C) Cu-Ni system
At TA: Only Liquid (L) TA A
tie line dus
i
WL = 100wt%, W = 0 1300 L (liquid) liqu
+ 
At TD: Only Solid () B L s
idu
TB sol
WL = 0, W = 100wt% R S
At TB: Both  and L 
1200 L+ D

TD (solid)
WL  C  Co  43  35  73wt % 20 3032 35 4043 50
C  CL 43  32 CLCo C
wt% Ni
Co  CL
W  = 27wt %
C  CL 26
Equilibrium Cooling of Cu-Ni Alloy
T(°C) L (liquid) L: 35wt%Ni
o Phase diagram: Cu-Ni
Cu-Ni system. 130 0
system
A
L: 35 wt% Ni
: 46 wt% Ni B
35 46
32 C
o Consider 43

microstructural 24 D L: 32 wt% Ni
36
changes that 120 0
: 43 wt% Ni
E
accompany the L: 24 wt% Ni
cooling of a : 36 wt% Ni

C0 = 35 wt% Ni alloy (solid)

110 0
20 30 35 40 50
C0 wt% Ni
27
o Conditions of equilibrium solidification and the development of
microstructures, are realized only for extremely slow cooling
rates

o The reason for this is that with changes in temperature, there

must be readjustments in the compositions of the liquid and
solid phases in accordance with the phase diagram (i.e., with
the liquidus and solidus lines.

o These readjustments are accomplished by diffusional

processes—that is, diffusion in both solid and liquid phases
and also across the solid–liquid interface. Diffusion is a time-
dependent phenomenon to maintain equilibrium

o During cooling, sufficient time must be allowed at each

temperature for the appropriate compositional readjustments.
Non-equilibrium Solidification
o The distribution of the two elements
within the grains is non-uniform, a
phenomenon termed segregation;

o The center of each grain, which is the

first part to freeze, is rich in the high-
melting element (e.g., nickel for this Cu–
Ni system), whereas the concentration
of the low-melting element increases
with position from this region to the grain
boundary. This is termed a cored
structure

o As a casting having a cored structure

is reheated, grain boundary regions will
melt first inasmuch as they are richer in
the low-melting component. Coring may
be eliminated by a homogenization heat
treatment carried out at a temperature
below the solidus point for the particular
alloy composition.
Cored Vs Equilibrium Phases
o Cα changes as it solidifies.
o 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
Uniform C  :
First  to solidfy:
46wt%Ni 35wt%Ni
Last  to solidfy:
< 35wt%Ni

o Coring can be eliminated by means of a homogenization heat treatment carried out at

temperatures below the alloy’s solidus. During the process, atomic diffusion produces
grains that are compositionally homogeneous.
Mechanical Properties: Cu-Ni System
o Effect of solid solution strengthening on:

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

Tensile Strength (MPa)

Elongation (%EL)
60
%EL for pure Cu
400 50 %EL for
pure Ni
TS for
pure Ni 40
300
30
TS for pure Cu
200 20
0 20 40 60 80 100 0 20 40 60 80 100
Cu Ni Cu Ni
Composition, wt%Ni Composition, wt%Ni

31
 Eutectic Alloys
o A eutectic or eutectic mixture is a mixture of two or
more phases at a composition that has the lowest melting
point.
o It is where the phases simultaneously crystallize from
molten solution. The proper ratios of phases to obtain a
eutectic is identified by the eutectic point on a binary
phase diagram.

o Not all binary system alloys have a eutectic point: those

that form a solid solution at all concentrations, such as
the gold-silver system, have no eutectic. An alloy system
that has a eutectic is often referred to as a eutectic
system, or eutectic alloy
o The term comes from the Greek 'eutektos', meaning
'easily melted.‘
32
o The phase diagram
displays a simple binary
system composed of two
components, A and B,
which has a eutectic point.

o The phase diagram plots

relative concentrations of A
and B along the X-axis, and
temperature along the Y-
axis. The eutectic point is
the point where the liquid
phase borders directly on
the solid α + β phase; it
represents the minimum
melting temperature of any
possible AB alloy.
o The temperature that corresponds to this point is known as the
eutectic temperature. Solid products of a eutectic transformation
can often be identified by their lamellar structure, as opposed to
the dendritic structures commonly seen in non-eutectic
solidification. 33
 Binary-Eutectic Systems
has a special composition
2 components with a min. melting T.
T(°C)
Cu-Ag system 1200
• 3 single phase regions L (liquid)
(L, , ) 1000
• Limited solubility:  L+ 
T 800 779°C L+ 
: mostly Cu E 8.0 71.9 91.2
: mostly Ag 600
• TE : No liquid below TE   
• CE : Composition at 400
temperature TE 200
0 20 40 60 CE 80 100
• Eutectic reaction C , wt% Ag
L(CE) (CE) + (CE)
cooling
L(71.9 wt% Ag) (8.0 wt% Ag)  (91.2 wt% Ag) 34
heating
Use of Gibbs Phase Rule
o For the Cu-Ag system @ 1 atm for a single
phase P:
C = 2 (Cu-Ag), P= 1 (α, β, l)
F = 2 -1 + 1 = 2
o This means that to characterize the alloy
within a single phase field, 2 parameters
must be given: temperature and
composition.
o If 2 phases coexist, for example, α +L , β
+L, α + β, then according to GPR, we have
1 degree of freedom: F = 2 -2+ 1 = 1. So, if
we have Temp or composition, then we can
completely define the system.

o If 3 phases exist (for a binary system), there are 0 degrees of freedom.

This means the composition and Temp are fixed. This condition is met
for a eutectic system by the eutectic isotherm.
35
Copper-Silver Phase Diagram
Pb-Sn Phase Diagram

Liquidus
Solidus Solidus

Solidus

Solvus Solvus
Determination of Phases Present, Phase Composition and
Weight fraction
o For a 40 wt% Sn-60 wt% Pb alloy at 150°C, determine:
-- the phases present Pb-Sn
T(°C)
Answer:  +  system
-- the phase compositions
300
Answer: C = 11 wt% Sn L (liquid)
C = 99 wt% Sn
 L+ 
-- the relative amount 200 183°C L+ 
of each phase 18.3 61.9 97.8
150
C - C0
W =  100
 C - C  + 

99 - 40 59
= = = 0.67
99 - 11 88 0 11 20 40 60 80 99100
W  = C0 - C C C0 C, wt% Sn C
C - C
40 - 11 29
= = = 0.33
99 - 11 88 38
Determination of Phases Present, Phase Composition and
Weight fraction
o For a 40 wt% Sn-60 wt% Pb alloy at 220°C, determine:
-- the phases present:
T(°C)
Answer:  + L
-- the phase compositions
300
Answer: C = 17 wt% Sn L (liquid)
CL = 46 wt% Sn L+ 
-- the relative amount 220 
200 L+ b
of each phase 183°C

CL - C0 100
46 - 40  + 
W = =
CL - C 46 - 17
6 0 17 20 40 46 60 80 100
= = 0.21 C C0 CL C, wt% Sn
29
C0 - C 23
WL = = = 0.79
CL - C 29
39
Microstructural Developments in Eutectic
Systems-I
T(°C) L: C0 wt% Sn
400

Pb-Sn System L

300 L
o For alloys where
L+ 
C0 < 2 wt% Sn 
200
TE : C0 wt% Sn

o Result at room temperature

is a polycrystalline with 100
+
grains of a phase having
composition C0
0 10 20 30
C0 C , wt% Sn
2
(room T solubility limit)
Microstructural Developments in Eutectic
Systems-II L: C 0 wt% Sn
T(°C)
400

Pb-Sn System L
L
300 
L+
: C0 wt% Sn
2 wt% Sn < C0 < 18.3 wt% Sn

200
TE

Results in polycrystalline 
microstructure with a grains
100
and small b-phase particles + 
at lower temperatures

0 10 20 30
2 C0 C, wt% Sn
(sol. limit at T room ) 18.3
(sol. limit at TE)
Microstructural Developments in Eutectic
Systems-III

Co = CE

Results in a
eutectic
microstructure
with alternating
layers of  and
 crystals. Pb-Sn
system

cooling
L(61.9 wt% Sn)  (18.3 wt% Sn)   (97.8 wt% Sn)
heating
 Lamellar Eutectic Structure
o A 2-phase microstructure
resulting from the solidification of
a liquid having the eutectic
composition where the phases
exist as a lamellae that alternate
with one another. Pb-rich

o Formation of eutectic layered Sn-rich

microstructure in the Pb-Sn
system during solidification at
the eutectic composition.
Compositions of α and β phases
are very different. Solidification
involves redistribution of Pb and
Sn atoms by atomic diffusion.

43
 Pb-Sn
Dark Microstructures
layers are lead-rich α phase. Light layers
are the tin-rich β phase.

44
Microstructural Developments in Eutectic
Systems-IV
Pb-Sn System
o For alloys with18.3 wt% Sn < C0 < 61.9 wt% Sn
o Result: a phase particles and a eutectic micro-constituent

T(°C) L: C0 wt% Sn
 L
L
300 L

L+ 
 
200 L+
TE 

100 +
Primary α
eutectic 
eutectic 
0 20 40 60 80 100
18.3 61.9 97.8
C, wt% Sn 45
Determination of Weight Fractions- Eutectic and Primary
constituents
Fraction of eutectic constituent is
just equal to fraction of liquid W L
from which it transforms
 • Just above TE :
C = 18.3 wt% Sn
T(°C) L: C0 wt% Sn CL = 61.9 wt% Sn
 L
L W Primary = CL - C0 = 0.50
300 L CL - C

L+  W L = (1- W  ) = 0.50

200 L+ 
TE  • Just below TE :
C  = 18.3 wt% Sn
100 +  C = 97.8 wt% Sn
Primary α
eutectic  W Cβ - C0
eutectic  total = C - C = 0.727
β 
0 20 40 60 80 100
18.3 61.9 97.8 W  = 0.273 wt% Sn
C, wt% Sn

47
Hypoeutectic and Hypereutectic Alloys
300
L
T(ºC)
 L+ 
200 L+ 
TE  (Pb-Sn
+ System)
100

0 20 40 60 80 100 C, wt% Sn
Eutectic
Hypoeutectic 61.9 Hypereutectic
Eutectic: C0 = 61.9 wt% Sn

 
 
   
 
 

Eutectic micro-constituent
48
Intermetallic Phases or Compounds

19 wt% Mg-81 wt% Pb

Mg2Pb

Note: intermetallic compounds exist as a line on the diagram - not a

phase region. The composition of a compound has a distinct chemical
formula. 49
Eutectic, Eutectoid and Peritectic
• Eutectic - liquid transforms to two solid phases
L cool  +  (For Pb-Sn, 183C, 61.9 wt% Sn)
heat

• Eutectoid – one solid phase transforms to two other solid

phases
Solid1 ↔ Solid2 + Solid3
cool
  + Fe3C (For Fe-C, 727C, 0.76 wt% C)
heat
• Peritectic - liquid and one solid phase transform to a 2nd
solid phase
Solid1 + Liquid ↔ Solid2
cool
 +L
heat
ε (For Cu-Zn, 598°C, 78.6 wt% Zn)

50
 Iron-Carbon System
o Pure iron when heated experiences two
changes in crystal structure before it
melts.
o At room temperature the stable form,
ferrite ( iron) has a BCC crystal structure.
o Ferrite experiences a polymorphic
transformation to FCC austenite ( iron) at
912 ˚C (1674 ˚F).
o At 1394˚C (2541˚F) austenite reverts
back to BCC phase  ferrite and melts at
1538 ˚C (2800 ˚F).
o Iron carbide (cementite or Fe3C) an
intermediate compound is formed at 6.7
wt% C.
o Typically, all steels and cast irons have
carbon contents less than 6.7 wt% C.
o Carbon is an interstitial impurity in iron
and forms a solid solution with the ,,
phases.
51
Iron-Carbon (Fe-C) Phase Diagram
• 2 important points T(ºC)
1600
- Eutectic (A): 
L   + Fe3C 1400 L

- Eutectoid (B):   +L
1200 A L+Fe3C
1148ºC
   + Fe3C (austenite)

Fe3C (cementite)
1000  
   +Fe3C
800 727ºC = T eutectoid
 B
600
 +Fe3C
120 mm 400
0 1 2 3 4 5 6 6.7
Result: Pearlite = 0.76 4.30
(Fe) C, wt% C
alternating layers of
 and Fe3C phases Fe3C (cementite-hard)
 (ferrite-soft) 52
Solid Phases
α-Ferrite
o Solid solution of carbon in α iron
o BCC structure
o Carbon only slightly soluble in the matrix
o Maximum solubility of 0.02% at 727 ̊C to about 0.008% at room temperature

Austenite (γ)
o Solid solution of carbon in γ-iron
o FCC structure; can accommodate more carbon than ferrite; maximum of 2.08%
at 1148 C, decrease to 0.8% C at 727 C
o Difference in C solid solubility between γ and α Is the basis for hardening of
most steels.

δ-Ferrite
o Solid solution of carbon in δ -iron
o BCC crystal structure
o Maximum solubility of ferrite being 0.09%C at 1495 C

Cementite (Fe3C)
o Intermetallic Fe-C compound
o Orthorhombic crystal structure: hard and brittle
Eutectoid reaction: Pearlite
↔  + Fe3C

Redistribution of carbon by diffusion

Austenite – 0.76 wt% C
Ferrite - 0.022 wt% C
Cementite - 6.70 wt% C
Hypo-eutectoid Steel
T(ºC)
1600

1400 L
  (Fe-C
  +L
  1200 1148ºC L+Fe3C System)

Fe3C (cementite)
(austenite)
 
1000
   + Fe3C
 800
  727ºC
  
600
 + Fe3C
400
 0 1 2 3 4 5 6 6.7
(Fe)C0 C, wt% C
0.76

pearlite

Hypoeutectoid
100 mm
steel

pearlite proeutectoid ferrite

Adapted from Fig. 9.30, Callister & Rethwisch 8e. 55
 Hypo-eutectoid Steel- Weight Fractions
T(ºC)
1600

1400 L
(Fe-C
  +L
 
 1200 1148ºC L+Fe3C System)

Fe3C (cementite)
 (austenite)
 
1000
 + Fe3C
W  = s/(r + s)
800 r s 727ºC
W  =(1 - W )
RS
 600
 + Fe3C
pearlite
400
0 1 2 3 4 5 6 6.7
(Fe)C0 C, wt% C
0.76

W pearlite = W 
W ’ = S/(R + S) 100 mm Hypoeutectoid
steel
WFe3C =(1 – W ’)
pearlite proeutectoid ferrite
Adapted from Fig. 9.30, Callister & Rethwisch 8e. 56
Hyper-eutectoid Steel
T(ºC)
1600

1400 L (Fe-C
  +L System)
 1200

 1148ºC L+Fe3C

Fe3C (cementite)
 (austenite)
  1000
   +Fe3C
Fe3C
  800
  
600
 +Fe3C
400
0 1 C0 2 3 4 5 6 6.7
0.76

(Fe) C, wt%C
pearlite

60 mmHypereutectoid
steel
pearlite proeutectoid Fe3C
Adapted from Fig. 9.33, Callister & Rethwisch 8e. 57
 Hyper-eutectoid Steel- Weight fractions
T(ºC)
1600

1400 L (Fe-C
 +L System)
Fe3C 1200

  1148ºC L+Fe3C

Fe3C (cementite)
(austenite)
  1000
 +Fe3C
W  =x/(v + x)
800 v x
WFe3C =(1-W )
 V X
600
 +Fe3C
pearlite
400
0 1 C0 2 3 4 5 6 6.7
0.76

(Fe) C, wt%C
W pearlite = W 
W  = X/(V + X)
60 mmHypereutectoid
WFe =(1 - W ) steel
3C’
pearlite proeutectoid Fe3C
Adapted from Fig. 9.33, Callister & Rethwisch 8e. 58
Example Problem
For a 99.6 wt% Fe-0.40 wt% C steel at a
temperature just below the eutectoid, determine
the following:

a) The compositions of Fe3C and ferrite ().

b) The amount of cementite (in grams) that forms
in 100 g of steel.
c) The amounts of pearlite and pro-eutectoid ferrite
() in the 100 g.

59
 Solution to Example Problem
a) Using the RS tie line just below the eutectoid
C = 0.022 wt% C
CFe3C = 6.70 wt% C

b) Using the lever rule with 1600

the tie line shown 
1400 L
R C  C T(ºC)
WFe 3C   0   +L

Fe3C (cementite)
R  S CFe 3C  C 1200 1148ºC L+Fe3C
(austenite)
0.40  0.022 1000
  0.057  + Fe3C
6.70  0.022
800 727ºC
R S
Amount of Fe3C in 100 g 600  + Fe3C
= (100 g)W Fe3C 400
0 1 2 3 4 5 6 6.7
Ca C0 C, wt% C CFe
3C
= (100 g)(0.057) = 5.7 g
60
Solution to Example Problem
c) Using the VX tie line just above the eutectoid and
realizing that
C0 = 0.40 wt% C
C = 0.022 wt% C
Cpearlite = C = 0.76 wt% C 1600

1400 L
V C  C T(ºC)
Wpearlite   0   +L

Fe3C (cementite)
V  X C  C 1200 1148ºC L+Fe3C
(austenite)
0.40  0.022 1000
 + Fe3C
  0.512
0.76  0.022
800 727ºC
VX
Amount of pearlite in 100 g 600  + Fe3C
= (100 g)W pearlite 400
0 1 2 3 4 5 6 6.7
Ca C0 C C, wt% C
= (100 g)(0.512) = 51.2 g
61
Alloying steel with other elements changes the Eutectoid
Temperature, Position of phase boundaries and relative
Amounts of each phase

62