Study of Alloy and Alloy Phase Diagrams

EMM 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 1

Phase :

 A homogeneous portion of alloy system that is physically distinct , chemically

homogeneous and mechanically separable from the other portion of the system.
 A physically homogeneous state of a matter

 Solid , liquid and gaseous phase

 Liquid solution – salt dissolved in water
 Solid solution – Solid solution of C in Iron

 Liquid phases are denoted by “L”

 Solid phases are denoted by Greek letters such as α, β, γ, δ and so on.

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 2

Component :

 It is a distinct chemical substance/species/element from which phase is formed.

 It is chemically distinct and essentially indivisible
 Generally components are pure elements such as Fe, C, Al, Ni etc.
 It may be a stable compound such as H2O , NaCl, and NiO etc. which may contain more
than one element.
 The combination of several components may constitute a single phase.
Example – Ni dissolved in Cu to form a solid solution
 A phase may have more than one component but reverse is not true i.e. a component can
not have more than one phase . But it is possible that a same component may exist as
another phase at a different temperature and pressure.
 Example - H2O
 (ice at 0 deg.C)
liquid between 0 to 100 deg.C
Vapour phase above 100 deg.C

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 3

Solid solution
It is a homogeneous mixture of two or more elements, where
one element is dissolved in another, typically in a metallic or
crystalline structure. In alloys, solid solutions play a crucial role
in determining properties such as strength, ductility, and
corrosion resistance.

1) Substitutional Solid Solutions 2) Interstitial Solid Solutions:

Solute atoms replace or substitute for the solvent Smaller solute atoms fit into the interstitial
atoms in the crystal lattice. spaces (gaps) between the solvent atoms in the
lattice.
Essential Conditions for formation: Essential Conditions for formation:
•Similar atomic radii (generally within 15%). • Solute atoms must be significantly
•Similar electronegativity. smaller than the solvent atoms.
•Same crystal structure. Example:
Example: Steel, where carbon atoms occupy interstitial
Brass, where zinc atoms substitute for copper atoms. spaces in the iron lattice.
Cu-Ni alloy system
The Humey Rothery Rules :
A set of empirical guidelines used to predict whether two metals (or
elements) can form a solid solution. These rules are particularly useful in
the context of alloy design, where the goal is to predict the solubility of
one element in another when forming a solid solution.

1) Atomic Size Difference:

The difference in atomic radii between the solute and solvent elements must be less than
15%. Example:
If the atomic size difference is too large, the solute atoms will distort the solvent’s crystal Copper-Zinc (Brass):
lattice, leading to reduced solubility or the formation of separate phases (not a solid solution).
 Zinc and copper
2) Crystal Structure:  Copper and Nickel
Both elements should have the same crystal structure (i.e., they should crystallize in the same
type of lattice, such as FCC, BCC, HCP, etc.).
If the crystal structures are different, it is less likely that a solid solution will form, and phase
separation may occur instead.

3) Electronegativity:
The electronegativity difference between the solute and solvent should be small.
A large difference in electronegativity tends to lead to the formation of intermetallic
compounds or phase separation, rather than a solid solution.

4) Valency (Chemical Bonding):

Elements with similar valency (i.e., similar number of valence electrons) are more likely to
form solid solutions. Elements of different valencies tend to form alloys with distinct phases
rather than a homogeneous solid solution.
Phase diagram
Graphical representation of different phases present in an alloy system at different
combinations of compositions, temperature and pressures.

Engineering Significance of phase diagram:

Enables one to identify the temperature – composition, temperature – pressure or

composition – pressure regions in which different phases are thermodynamically stable.

It is possible to obtain the number of phases , their compositions, and the relative
proportions of phases as a function of temperature, pressure and overall composition.

Also referred as constitution diagram / equilibrium diagram.

If nothing is specified , a phase diagram is referred as equilibrium phase diagram.

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 6

Representation and types of phase diagram

Unary phase diagram

Phase diagram for pure metal.

Unary alloy – only one
component.

Composition is fixed
Pressure and temperature are
variable

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 7

Binary phase diagram

Phase diagram for binary alloy

binary alloy – two component.

Pressure is fixed or assumed

constant i.e. at atm

Composition (i.e. weight

percent of B in A) and
temperature are variable

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 8

Ternary phase diagram
Phase diagram for ternary alloy
ternary alloy – three component.

Pressure is fixed or assumed constant

i.e. at atm

Temperature is also fixed.

Most operations are carried at room

temperature and pressure.

Composition is variable
 weight % of B in A
 Weight % of C in A
 Weight % of C in B

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 9

 Gibbs Phase Rule
 Gives a relationship between number of components and
phases present in an alloy system under the given conditions
of temperature and pressure.

 Determines number of phases (P) that can coexist at Degrees of freedom(F):

equilibrium with the minimum number of components (C)
that can be used to form the alloy system and degrees of Number of independent variables
freedom (F). such as temperature , pressure
and composition that can be
P+F=C+2 changed without changing the
 For condensed phase i.e. solid and liquids , the phase rule can number of phases for the given
be written as, number o components.

P+F=C+1
EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 10
EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 11
 Invariant Points

 Point on alloy phase diagram at which degrees of Freedom (F) = 0

 Invariant points in any alloy phase diagram helps in identifying maximum number of
phases that could coexist under equilibrium conditions at given temperature and
composition.

P =C +1 since P + F = C + 1 and F =0

 Unary Alloy system , P = C + 1 = 1+1 =2

 Binary Alloy system , P = C + 1 = 2+1 =3
 Ternary Alloy system , P = C + 1 = 3+1 =4

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 12

Invariant Reactions

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 13

Isomorphous Binary Phase Diagram

Crystal structure of the

two component and solid
solutions are same and
also system exhibits
complete solubility in
solid as well as liquid
state.

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 14

Tie line rule for determining composition of phases
 Used to identify the composition
of constituent phases
 Tie line is constant temperature
line of interest
 Co overall composition of alloy in
binary phase
 Intersection of tie line with solidus
curves gives composition of solid
phase (Cα) and intersection of tie
line with liquidous curve gives the
composition of liquid (CL)
 Same rule is applicable of two
phase region containing two solid
phases or two liquid phases

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 15

Lever rule for determining fraction/percentage of each phases

 Used to determine the

amount ( fraction or
percentage) of constituent
phases in two phase region

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 16

The fraction/amount/percentage of liquid phase is determined by
taking the length of tie line away from the liquid phase and dividing it
by total length of tie line.

𝐶0−𝐶α
Fraction of liquid phase, fL = and percentage liquid = fL *100
𝐶𝐿−𝐶α

The fraction/amount/percentage of solid phase is determined by taking

the length of tie line away from the solid phase and dividing it by total
length of tie line.

𝐶α−𝐶0
Fraction of liquid phase, fα = and percentage liquid = fL *100
𝐶𝐿−𝐶α

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 17

Allotropic forms of Pure Iron/ Polymorphism in Pure Iron :

Allotropy or Polymorphism
is a phenomenon where
element/compound may
exist in more than one
crystallography form der
different conditions of
temperature and pressure.

Curie Temperature:
Ferromagnetic to Paramagnetic conversion and
vice versa.

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 18

Study of Iron – Iron Carbide Phase diagram

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 19

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 20
  Continuous line represent
Iron – Iron Carbide phase
diagram.
i.e. Fe – Fe3C

 Dotted lines indicate

phase diagram
corresponding to stable
graphite phase
 i.e. Fe-C equilibrium
phase diagram

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 21

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 22
 Various Phases observed on Iron-Iron Carbide Phase Diagram

α- Ferrite phase:
 Definition: It is an interstitial solid solution of carbon in α-iron.
 Crystal Structure : BCC
 Temperature Stability:- -273 0C to 912 0C
 Maximum solid solubility limit of carbon in α-Fe : 0.021 wt. % at the eutectoid temperature of 727 0C

Note : Carbon is present at the interstitial sites of Fe matrix. The size of largest atom that can fit in this
interstitial position is 0.19A0 , which is much small than the size of carbon atom i.e. 0.71A0 . Hence the
solubility carbon atom is extremely limited in BCC Iron.

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 23

γ (Austenite) phase:
 Definition: It is an interstitial solid solution of carbon in γ-iron.
 Crystal Structure : FCC
 Temperature Stability:- 912 0C to 1394 0C
 Maximum solid solubility limit of carbon in γ-Fe : 2.1 wt. % at the eutectic temperature of 1147 0C

Note : Carbon is present at the interstitial sites of Fe matrix. The size of largest atom that can fit in this
interstitial position is 0.52A0 , compared with the size of carbon atom i.e. 0.71A0 . Hence the solubility
carbon atom is higher compared to BCC Iron.

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 24

δ – Ferrite phase:
 Definition: It is an interstitial solid solution of carbon in δ-iron.
 Crystal Structure : BCC
 Temperature Stability:- 1394 0C to 1539 0C
 Maximum solid solubility limit of carbon in δ-Fe : 0.09 wt. % at the peritectic temperature of 1492 0C

Cementite (Fe3C)phase:
 Definition: It is an intermetallic compound of iron and carbon with chemical formula of Fe3C .
 Crystal Structure : complex orthorhombic crystal structure with twelve Iron atoms and four carbon
atoms in its unit cell
 Maximum solid solubility limit of carbon : It can dissolve maximum of 6.67 wt. % of carbon

Graphite (free carbon)phase:

 It has hexagonal crystal structure in which sheets primary bonded carbon atoms are held together by
weak secondary bonds.

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 25

 Invariant Reactions observed on Iron-Iron Carbide
Phase Diagram

Peritectic Reaction:
Using Lever Rule, it is observed that Peritectic
composition consists of 82.2 % percentage δ-
ferrite phase and 17.8 % liquid Fe-C phase.

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 26

 Eutectoid Reaction

Using Lever Rule, it is observed that

Eutectoid composition consists of 88.8 %
percentage α-ferrite phase and 11.2 % liquid
Cementite phase. This eutectoid mixture is
known as pearlite.

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 27

 When this Eutectoid composition i.e. pearlite
cooled to room temperature , amount of
ferrite will go on decreasing and amount of
cementite will go on increasing till room
temperature. Hence at room temperature
pearlite Consists of 88.71 % percentage α-
ferrite phase and 11.29 % liquid Cementite
phase. This eutectoid mixture is known as
pearlite.

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 28

Eutectic Reaction:

Using Lever Rule, it is observed that Eutectic

composition i.e. ledeburite consists of 51.85 %
percentage γ- austenite phase and 48.15 %
cementite phase.

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 29

 Transformed Ledeburite:
The austenite from ledeburite is not stable
below 727 0C and hence it transformed to
pearlite. Thus at room temperature
structure consists of mixture of pearlite and
cementite known as transformed ledeburite.
Using Lever Rule, it is observed that
transformed ledeburite consists of 40.4 %
percentage pearlite phase and 59.6 %
cementite.

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 30

Important Note:
Out of these three invariant reactions observed on Iron- Iron Carbide Phase diagram,
 Peritectic reaction is least important for commercial applications, since steel is rarely heated to high
temperature where peritectic reaction occurs.
 Eutectoid reaction is most important since steels are heated to and above the eutectoid temperature so
that steel exist in austenitic condition, from where it is cooled at controlled rate to get different
microstructures and hence different mechanical properties.
 Eutectic reaction is important Cast Irons.
 Hypo eutectoid Steels : Steel with carbon content less than Eutectoid composition i.e. 0.76 wt. %
 Hyper eutectoid Steels : Steel with carbon content greater than Eutectoid composition i.e. 0.76 wt. %
 Hypo eutectic Cast Iron : Cast Iron with carbon content less than Eutectic composition i.e. 4.3 wt. %
 Hyper eutectic Cast Iron : Cast Iron with carbon content greater than Eutectic composition i.e. 4.3 wt. %

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 31

 Critical Temperatures observed on Iron-Iron Carbide Phase
Diagram
Temperature at which phase change occurs during heating and cooling are known as critical temperatures:
A0 : 210 0C
 At this temperature cementite changes from magnetic to non magnetic character and vice-versa.
 Known as Curie temperature for cementite.
A1 : 727 0C (Eutectoid Temperature)
 At this temperature pearlite transforms to austenite during heating and vice versa.
 This temperature line is not a Function of carbon content i.e. does not depend upon the carbon content.
A2 : 768 0C
 It is the curie temperature of iron
 Ferrite undergoes magnetic transition from ferromagnetic to paramagnetic on heating.
 This temperature line is function of carbon content

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 32

A3 :
 This temperature line decreases from 910 0C at 0 wt. % of C to 727 0C at 0.76 wt. % of C and then it is
constant 727 0C up to 6.67 wt. %
 It is the temperature corresponds to (α+γ )/ γ phase boundary for hypo-eutectoid steel where last trace
of free α-ferrite get dissolved to form 100% Austenite.
 This temperature line is a function of carbon content.
Acm :
 This temperature line increases from 727 0C at 0.76 wt. % of C to 1147 0C at 2.1 wt. % of C .
 It is the temperature corresponds to γ / (γ + Fe3C) phase boundary for hyper-eutectoid steel where last
trace of free cementite get dissolved to form 100% Austenite.
 This temperature line is function of carbon content and more steeper than A3 temperature line.

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 33

A4 :
 This temperature line is a function of carbon content.
 This temperature line Increase from 1400 0C at 0 wt. % of C to 1492 0C at 0.09 wt. % of C
 It is the temperature corresponds to (δ+γ )/ γ phase boundary where last trace of austenite get
dissolved to form 100% δ-ferrite .

 A1 : Lower Critical temperature

 A3 : Upper Critical Temperature for Hypo-eutectoid steel
 Acm : Upper Critical Temperature for Hyper-eutectoid steel

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 34

 Slow Cooling behaviour and Pearlite is lamellar mixture of α-ferrite and
microstructural changes during cementite which is observed just below
cooling of 0.76 wt.% carbon steel eutectoid point. While cooling through
from austenite state to room eutectoid temperature , austenite with 0.76
wt.% C phase decomposes to low carbon α-
temperature(Eutectoid steel) ferrite phase (0.022wt.% C) and high
carbon cementite phase (6.67Wt.% C) i.e.
redistribution of carbon is taking place and
this happens through diffusion process.
Ferrite phase will form where depletion of
carbon is there and cementite phase will
form at carbon rich zone. The carbon atom
will diffuse away from the ferrite phase
enriching the neighbourhood with carbon
and therefore the cementite phase will
form surrounding the ferrite phase. Thus
ferrite and cementite phase nucleate
alternatively resulting in the formation of
lamellar structure of pearlite.
Nucleation and Growth of Pearlite
EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 35
 Austenite (eutectoid) Contains 0.76 wt.% C
 During eutectoid reaction at 727 deg.C temperature, this carbon from austenite diffuses
(redistributes) to low carbon alpha ferrite phase and high carbon cementite phase.
 In austenite phase , it is possible that, at some point there is low carbon and at some point there
is high carbon. Low carbon region is favorable for the nucleation of ferrite and high carbon region
is favorable for the formation of cementite.
 Assuming there is low carbon region (carbon depletion), austenite will form ferrite nucleate at this
point by diffusing away carbon from it. This enriches the carbon in the neighborhood of ferrite.
This carbon rich region, now, it is favorable for cementite and hence cementite is formed by
consuming carbon from the surrounding region. Now, there is low carbon surrounding cementite
and hence it is again it is favorable for ferrite nucleation. This process will continue to yield
alternation layers of ferrite and cementite i.e. Pearlite
 Pearlite is lamellar mixture of alternate layers of alpha ferrite and cementite. Application of lever
rule for the pearlite gives 88.9 % of ferrite and 11.1 % cementite i.e. in pearlite , ferrite and
cementite are present in the ration 8:1 . Hence ferrite layer looks thicker and cementite layer
looks thinner.
 If the magnification and resolution is low, then pearlite microstructure may not always shows well
resolved layers of ferrite and cementite. It looks like simply a dark mass.
 But if magnification and resolution is high enough, then one can clearly see the alternate layers of
ferrite and cementite.
EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 36
 Unresolved pearlite

Representative sample of pearlite

Well resolved pearlite
EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 37
EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 38
EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 39
EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 40
Slow Cooling behaviour and microstructural
changes during cooling of 0.3wt.% carbon steel
from liquid state to room temperature(Hypo-
eutectoid steel)

Hypo-eutectoid : Between 0.22 and 0.76 Wt.% C

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 41

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 42
 point 1-2: FeC alloy is in liquid state. Alloy will remain in liquid state till point 2.
 point 2-3: at point 2, Solidification process starts and δ-ferrite nucleates in the liquid. This process
continues till point 3.
 Point 3-4: Just below point 3 , liquid with 0.55 wt. %C and δ-ferrite with 0.09wt.% carbon undergo
peritectic reaction to yield austenite with 0.18 wt.% carbon. From point 3 to 4, microstructure now
contains austenite and liquid FeC. From point 3-4 , the carbon contain in the austenite increasing and in
the liquid FeC it is decreasing. from 0.18 wt. % at 1492 0C to 2.1 wt.% at 1147 0C.
 At point 3 , there is 55.56 % δ-ferrite and 44.44% liquid FeC is present.(Obtained by lever rule)
 Point 4-5 : just below point 4 , the remaining liquid Fe-C forms γ phase and this phase will continue till
point 5.
 Point 5-6 : just below point 5, α-ferrite start separating out at the grain boundaries austenite since
carbon content in the austenite start decreasing. As temperature decreases , amount α-ferrite
increases. This α-ferrite is known as proeutectoid ferrite. This process continues till point 6 and carbon
content in the austenite decreases to 0.76 Wt.%.
 Point 6-7: Just below point 6, since austenite is not stable , it transforms to pearlite. At this point
microstructure consists of 62.5% proeutectoid ferrite and 37.5% pearlite (obtained by lever rule). With
decreasing temperature from 727 0C to room temperature , there is no significant change in the
microstructure is observed except decrease in the ferrite content and increase in the cementite
content since solubility of carbon in α-ferrite is decreasing.
 At room temperature , 0.3 wt % hypo eutectoid steel contains , 95.61 % amount of cementite and
4.39% amount of ferrite (Obtained by lever rule).

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 43

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 44
Slow Cooling behaviour and microstructural
changes during cooling of 1.3wt.% carbon steel
from liquid state to room temperature(Hyper
eutectoid steel)

Hyper-eutectoid : Between 0.76 and 2.1 Wt.% C

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 45

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 46
EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 47
Slow Cooling behaviour and microstructural
changes during cooling of Eutectic Cast Iron with
4.3 wt% C)

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 48

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 49
Slow Cooling behaviour and microstructural
changes during cooling of Hypo Eutectic Cast Iron
with 3 wt% C)

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 50

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 51
Slow Cooling behaviour and microstructural
changes during cooling of Hyper Eutectic Cast Iron
with 5 wt% C)

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 52

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 53
EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 54
EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 55
 Types of Cast Irons with respect Iron-Iron carbide
phase diagram
 Cast Iron :- alloy of iron and carbon containing 2.1 to 6.67 wt.% carbon
 Very brittle due to high carbon content
 Commercially manufactured cast irons contains 2.5 to 4.5 wt.% carbon

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 56

General Properties of cast irons:
 Very low ductility – can not be rolled, drawn and worked room temperature.
 Not malleable at room temperature
 Melt easily and can be cast into complicated shapes which are usually machined to
final dimensions. (lower melting point)
 Brittle and lower strength properties
 Cheap
 Properties can be altered by proper alloying, good foundry control and appropriate
heat treatment

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 57

Types of cast irons:
 Classified on the basis of metallographic structure
 Variables which leads to variety of cast irons are:
Carbon content , alloy and impurity content, cooling rate during and after freezing ,
heat treatment after casting etc.
 Carbon may be combined as iron carbide in cementite form or it may exist as free
carbon in graphite form. The shape and distribution of free carbon greatly
influences physical properties

White CI, Malleable CI, Grey CI, Nodular CI,

Meehanite CI, Alloy CI
EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 58
 White Cast Iron:
Consider slow cooling behaviour
and microstructural changes
during cooling of hypoeutectic
cast iron with 3.0 wt.% carbon

 Hypoeutectic C.I. (2.1 – 4.3 wt.% C)

 Eutectic C.I. (4.3 wt.% C)
 Hyper eutectic C.I. (4.3-6.67 wt.% C)

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 59

 Point 1-2:
The Fe-C alloy is in liquid state and there is no
change in microstructure till point 3.

Point 2-3:
Just below point 2, the austenite start
separating out from liquid and further cooling
increases the amount of austenite. This
continues up to point 3. This austenite is
known as primary or pro eutectic austenite
and is in the dendritic form since it is
separating out from liquid. The carbon
content in the liquid decreases to eutectic
composition.

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 60

 Point 3-4:
Just below point 3, the liquid Fe-C alloy with eutectic
composition i.e.4.3 wt.% C at 1147 0C solidifies forms
an eutectic mixture of austenite and cementite
known is ledeburite. Thus the composition to the left
of eutectic composition contains proeutectic
austenite in addition to the ledeburite.

Just below point 3

4.3−3.0
% proeutectic austenite = *100 = 56.5%
4.3−2.1
% Ledeburite = 43.5 %

Just above point 3

4.3−3.0
% proeutectic austenite = *100 = 56.5%
4.3−2.1
% liquid = 43.5 %

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 61

Point 3-4 (continued):

 Just below point3 , microstructure consists of primary/proeutectic

austenite and ledeburite.
 There is no change in the morphology of existing microstructure till
point 4. however the solubility of carbon in austenite from 2.11 wt.% C
at 1147 0C to 0.76 wt.% C at 727 0C . Due to this both primary and
eutectic austenite rejects excess carbon. This excess carbon precipitates
as cementite to the adjacent cementite areas. Hence amount of
cementite increases. This excess cementite which precipitates out is
called proeutectoid cementite. Hence just above point , morphology
consists of primary/proeutectic austenite, ledeburite and proeutectoid
cementite.

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 62

 Point 4-5:
 Just below/at point 4 ,during cooling through
eutectoid temperature of 727 0C , all the austenite
(both primary as well as eutectic) decomposes to
eutectoid mixture of α-ferrite and cementite
known as pearlite. Hence microstructure of cast
iron below point 4 consist of pearlite and
proeutectoid cementite. There is no change in the
microstructure till point 5 except marginal increase
in the amount of cementite due to decrease in
solubility of carbon in ferrite.

Note: in the above description, all the carbon is present in the combined form
i.e. Cementite and the alloy is called white cast iron as fracture surface of such
component material looks white.

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 63

Important features of White Cast Iron:
 All the carbon is present in the form of combine carbon i.e. cementite (Fe3C)
 There is no free carbon i.e. graphite
 The appearance of fracture surface is white because of absence of graphite
and hence the name is white cast iron.
 Since there is no graphitization, the solidification of white cast iron and the
resultant microstructural changes can be exactly indicated on iron-iron carbide
equilibrium phase diagram.
 The graphitization can be supressed by controlling chemical composition and
cooling rate.

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 64

Important Properties of White Cast Iron:
 Due to the presence of large amount of cementite as interdendritic network, white cast
irons are brittle and hard.
 Hardness increases with increasing carbon content and makes cast iron extremely brittle
which is not suitable for engineering applications. Therefore majority of cast irons are
hypo-eutectic with usual composition:
C = 2.3 to 3 %, Si = 0.5 -1.3 %, S = 0.06-0.1 %, P = 0.1-0.2 5, Mn= 0.5-0.1 %
 Hardness : 350-500 BHN
 Strong in compression : compressive strength = 140 -175 kg/mm2
 Excellent wear resistance
 Difficult to machine. Hence finishing to final shape and size is done by only grinding i.e.
lack of machinability

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 65

Important Applications of White Cast Iron:

 Balls for grinding mills

 Liners for cement mixtures
 Rolls for paper manufacturing
 Wearing plates
 Pump liners
 Mill liners
 Dies and extrusion nozzles
 Used for production of malleable cast iron
 Not employed for structural applications due to excessive brittleness.

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 66

Important Properties of White Cast Iron:
 Due to the presence of large amount of cementite as interdendritic network, white cast
irons are brittle and hard.
 Hardness increases with increasing carbon content and makes cast iron extremely brittle
which is not suitable for engineering applications. Therefore majority of cast irons are
hypo-eutectic with usual composition:
C = 2.3 to 3 %, Si = 0.5 -1.3 %, S = 0.06-0.1 %, P = 0.1-0.2 5, Mn= 0.5-0.1 %
 Hardness : 350-500 BHN
 Strong in compression : compressive strength = 140 -175 kg/mm2
 Excellent wear resistance
 Difficult to machine. Hence finishing to final shape and size is done by only grinding i.e.
lack of machinability

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 67

 Malleable Cast Iron
 Produced from malleable cast iron by a malleablizing heat treatment.
1. Slow heating of white cast iron castings
(to avoid cracking) to a temperature
between eutectoid and eutectic
temperature , usually around 800-950 0C .

2. Holding the castings at this temperature

for a longer duration (24 hours to several
days)

3. Slow cooling to room temperature.

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 68

 Malleable Cast Iron (Continued…)
 At 800-950 0C, the microstructure consists of austenite and cementite and
cementite is a metastable phase. This cementite decomposes to more stable
forms i.e. austenite and graphite. The graphite is free carbon and precipitates
in the form spheroidal particles called as temper carbon.(note particles are
not truly spherical).
 Graphitization of cementite gives rise to rough, ragged irregular nodules /
spheroids known as rosettes of temper carbon.
 Therefore at point 2, microstructure consists of rosettes of temper carbon i.e.
graphite in a matrix of austenite.
 Cooling to a room temperature with high/moderate cooling rate results in
transformation of austenite to pearlite at eutectoid temperature. Therefore at
point 3 structure shows rosettes of temper carbon in the matrix of pearlite

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 69

Malleable Cast Iron (Continued…)
 If the cooling rate is slow (or silicon percent in the white castings is more),
then cementite from pearlite may also decomposes giving ferrite and graphite.
Hence, in this condition ,the microstructure at room temperature may shows
rosettes of temper carbon in the matrix of ferrite.
 For intermediate conditions , matrix may shows presence of both ferrite as
well as pearlite.
 Thus malleable cast irons are divided into three types:

1. Pearlitic malleable
2. Ferritic malleable
3. ferrito-pearlitic malleable cast iron.

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 70

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 71
Properties of Malleable Cast Iron:
 Tensile strength up to 700 MPa with an elongation of 10-15%
 More expensive because of heat treatment involved
 All other properties are similar to white cast iron

Applications of Malleable Cast Iron:

 Automobile crank shaft

 Chain links
 brackets

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 72

Grey Cast Iron
 When the graphite is present in the form of flakes ,the fracture surface
looks grey and the alloy is called Grey C.I.

Factors that promote graphite formation:

 Slow cooling or freezing

 Addition of Si
 Increasing carbon content in the melt
 Non Carbide forming elements such as Cu, Ni, Al have positive impact
 Carbide forming elements such as Cr, Mn, Mo, have negative impact

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 73

Microstructure:

Graphite flakes embedded in ferrite or pearlite matrix. Flakes are nothing

but curved plates interconnected in three dimension.

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 74

Properties of Grey CI:

 Cheapest of all the ferrous alloys since temperature to be attained for making it is
several hundred degrees lower than that of casting steel and also control of
impurity is not critical as in case of steel making
 Easiest to cast due to high cast ability resulting from low melting point
 Excellent machinability. Easy to machine since chip formation is promoted by
graphite flakes. In addition graphite flakes serves as lubricant for cutting tool.
 Good compressive strength
 Good bearing properties
 Fairly good corrosion resistance
 Good fluidity of melt and low shrinkage during solidification
 Takes mould impression quite well
 Superior damping capacity that of steel

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 75

Properties of Grey CI: Drawbacks of Grey CI:
 Graphite flakes are sharp at their tip and acts like
General Composition: internal stress or crack raisers, hence these are brittle
C = 3.2 to 5.7 % and shows only 0.5 % elongation in tension
Si = 2.0 -3.5 %  As cracks do not propagate under compressive loads,
S= 0.06 -0.1 % the strength is more in compression than tension
P = 0.1-0.2 %  growth or permanent expansion occurs when heated
Mn = 0.5-1.0 % to about 400 deg.C . This results in loss of strength and
brittleness.
TS = 15-40 kg/mm2  Repeated local heating and cooling to temperature of
Hardness = 150-300 BHN order 550 degree C , fire cracks or heat cracks occur in
% Elongation: less than 1% the form of cracks. i.e. high thermal gradient between
surface and interior, may lead to failure of component.
 this drawback can be reduced by the addition of
certain alloying elements like Cr, Mo, Ni etc. but due to
this cost tend to increase

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 76

Application of Grey CI:

 A bases for erecting machinery i.e. machine bases (good damping capacity and
high compressive strength)
 Locomotive and IC engine cylinder blocks and heads (ease machining, good
damping capacity, and wear resistance)
 Flywheel and counterweights for lift (ease casting and low cost)
 Engine frames , draining pipes and pump housing

Examples:
Ni Hard Iron = 4 % Ni, 1.5 % Cr
Ni Resist = 20% Ni, 2 % Cr

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 77

Types of Grey CI depending upon the matrix :

 If the cooling rate is fast and if

only part of carbon is present in
the form of graphite flakes , we
have pearlitc grey Cast Iron

 If all the carbon is present in the

form of graphite and if the
cooling rate is very slow, then
we have ferritc Grey Cast Iron

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 78

 Types of Grey CI depending upon the distribution of graphite flakes :

Type A: Uniform Distribution, Fine and randomly oriented According to American Foundry
Type B: Rosette Grouping , Random Orientation men’s association (AFM) and
Type C: Superimposed flakes of mixed sizes with random American Society for Testing and
orientation Materials (ASTM)
Type D:Interdenrtic Segregation, Randomly Orientated
Type E: Interdendrtic Segregation, Preferentially oriented

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 79

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 80
Microstructural control:
 The composition of alloy is adjusted in such way that all the proeutectic and
eutectic cementite decomposes to graphite as soon as it forms and
eutectoid cementite does not decompose. This is done by controlling
carbon and silicon in the alloy. If the C an Si amount is more, eutectoid
cementite may also decompose with normal cooling rates as encountered
in sand moulds. This leads to ferrite matrix and cast iron becomes soft and
extremely weak and thereby not being suitable for engineering application,
therefore the control over the composition is very much essential.

 Slow cooling rate promote graphite formation. Thick cross sections in the
casting tends to have graphite(slow cooling) and thin cross section tends to
have cementite.

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 81

 Nodular/ Spheroidal Graphite (SG) Cast Iron
 Contains graphite in the form of nodules or spheroids
 Here graphite nodules are truly spherical in contrast to irregular
aggregate of temper carbon in case of malleable cast iron

 These cast irons are produced by adding small quantities of certain

elements called as modifiers or nodulizing agents such as Mg,
Cerium, Barium, Lithium, or zirconium to the melt.

 Universal modifier : Mg (most common) = 0.06 to 0.08 %

 Modifier has the effect of making the growth rate of graphite to be
approximately same in all direction, so that a spherical shape results

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 82

 Though magnesium is universal modifier, it has low density and it is
highly reactive. If they are added in pure form, simply they float to
the top of melt bat and burn or decompose at the surface. Therefore
they are usually added in the form of master alloys.
 Example: Mg is added in the form Ni-Mg alloy where Ni is also
Graphitizer

 Also, these modifiers have strong affinity for sulphur and they
scavenge sulphur from the molten bath. And these sulphur additions
are expensive and hence for effective utilization of these elements,
the original grey iron melt must contain less amount of sulphur (<
0.03 %).

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 83

 When modifier is added to molten bath and stirred, large amount of
gas is evolved and also get dissolved in the melt. This dissolved gas
gives rise of blow holes in the solidified casting.

 Also during the solidification, the contraction of nodular CI is

considerably significant than ordinary grey cast iron.

 Design of mould is necessary to avoid shrinkage cavities in the

castings.

 Good control of melt charge is essential to keep residual and

impurity elements within specified limits

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 84

 Mg is added to grey CI melt usually in the ladle just prior to pouring
into the mould. Any delay in pouring results in distortion of nodular
shape of graphite and reduction in the properties of grey cast iron.
 The effect of nodulizing agent is purely temporary and is lost due to
longer holding.
 Remelting of nodular cast iron produces Grey C.I.
 The Mg alloy is added in the form of capsule and the ladle is sealed
with cover to prevent Mg vapour from escaping .
 The residual magnesium in the casting is about 0.05 %
 The mechanism by which graphite nodules are formed is not known
certainly. It is postulated that, the addition of nodulizing element
may be affecting the surface favouring the nodule formation.

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 85

Microstructure :
The matrix of nodular
cast iron can be
controlled by
controlling the
composition, i.e. C and
Si and by cooling rate

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 86

Nodular/ Spheroidal/ Bull’s eye structure in SG Iron

EMM MODUEL 3_STUDY OF ALLOY AND ALLOY PHASE DIAGRAMS 87