ME2200

Ratna Kumar Annabattula,

MDS - 208
Phase Diagrams Dept. Mech. Engg.
IIT Madras
ratna@iitm.ac.in
 Learning Objectives
❖ Sketch simple isomorphous and eutectic phase diagrams;
label various regions, liquids, solidus and solvus lines.
❖ Determine
❖ the phase present
❖ composition of phases
❖ mass fraction of phases,
given a binary phase diagram, composition of the alloy, its
temperature by assuming that the alloy is at equilibrium.
 Learning Objectives
❖ Label all phases, reactions in a given binary phase diagram.
❖ Draw the microstructures of an alloy when it is cooled slowly
from molten state to room temperature at a given alloy
composition.
❖ Draw the schematic of Fe-Fe3C equilibrium phase diagram
and label all the phases and temperatures which denote all
phase transformations.
❖ Determine whether an alloy is hypoeutectoid or
hypereutectoid given the weight percent of carbon in Fe-Fe3C
equilibrium diagram
Materials Engineering Workflow
Materials Engineering Workflow
Material scientists are “god-like”
for their contribution to alloys
Why pure metals are alloyed?
 Why pure metals are alloyed?
❖ Yield and tensile strength can be increased
 Why pure metals are alloyed?
❖ Yield and tensile strength can be increased
❖ increase hardness
 Why pure metals are alloyed?
❖ Yield and tensile strength can be increased
❖ increase hardness
❖ melting point of the solvent (base metal) can be increased
 Why pure metals are alloyed?
❖ Yield and tensile strength can be increased
❖ increase hardness
❖ melting point of the solvent (base metal) can be increased
❖ strength of the solvent at high temperature can be
dramatically increased
 Why pure metals are alloyed?
❖ Yield and tensile strength can be increased
❖ increase hardness
❖ melting point of the solvent (base metal) can be increased
❖ strength of the solvent at high temperature can be
dramatically increased
❖ improve corrosion resistance
 Why pure metals are alloyed?
❖ Yield and tensile strength can be increased
❖ increase hardness
❖ melting point of the solvent (base metal) can be increased
❖ strength of the solvent at high temperature can be
dramatically increased
❖ improve corrosion resistance
❖ improve manufacturability
 Why pure metals are alloyed?
❖ Yield and tensile strength can be increased
❖ increase hardness
❖ melting point of the solvent (base metal) can be increased
❖ strength of the solvent at high temperature can be
dramatically increased
❖ improve corrosion resistance
❖ improve manufacturability
❖ melting point of base metal can be lowered
Alloys and their limitations
 Alloys and their limitations
❖ There is a limit on how much of solute can go into
solution!
 Alloys and their limitations
❖ There is a limit on how much of solute can go into
solution!
❖ How do they fit into the solvent cloud?
❖ Substitutionally
❖ Interstitially
 Alloys and their limitations
❖ There is a limit on how much of solute can go into
solution!
❖ How do they fit into the solvent cloud?
❖ Substitutionally
❖ Interstitially
❖ What happens to a solvent as increasing amount of
particular solute atom is added?
 Alloys and their limitations
❖ There is a limit on how much of solute can go into
solution!
❖ How do they fit into the solvent cloud?
❖ Substitutionally
❖ Interstitially
❖ What happens to a solvent as increasing amount of
particular solute atom is added?
❖ The answer to the most important last question is
answered by phase diagrams
Language of Phase Diagrams
 Basic Definitions
❖ Component: Pure metals and/or compounds of which an
alloy is composed
❖ System: Series of possible alloys consisting of the same
components, but without regard to alloy composition
(e.g, iron-carbon system)
❖ Phase: Homogeneous portion of a system that has
uniform physical and chemical characteristics
❖ Homogeneous system: single phase
❖ Mixture or Hetrogeneous system: multiple phases
 Basic Definitions

❖ Solvent: Component in large proportion or the “host”

❖ Solute: Component that gets dissolved or the “guest”
 Solubility limit
❖ At a specific temperature, the
maximum concentration of solute
atoms that may dissolve in the solvent
to form a solid solution
❖ Sugar-Water system
❖ Red curve show solubility limit
❖ left to red curve the system is liquid
solution
❖ right to red curve liquid solution and
solid sugar co exist
❖ Solubility limit increases with increase
in temperature
 Basic definitions
❖ Equilibrium: A system is in equilibrium if its free energy
is at a minimum. Macroscopically, the characteristics of
the system do not change with time
❖ Phase equilibrium: Constancy of phase characteristics with
time (see what happens to sugar syrup at say 30oC in
contact with solid sugar if heated to 100oC suddenly)
❖ Metastable state: Non-equilibrium state but with very
long time for changes to occur

Perfect equilibrium does not exist!

 Introduction

❖ Properties of a material to a large extent depend on

❖ type, number, amount and form of different phases
❖ Important to know
❖ Conditions for existence of the phases
❖ Conditions for change of phases
 Introduction

❖ Phase changes in many alloy systems is best described

through Phase Diagrams (also called equilibrium or
constitutional diagrams)
❖ Physical properties required for complete description of
equilibrium: pressure, temperature and composition
One-component (Unary) Phase Diagram

O
One-component (Unary) Phase Diagram
Phase boundaries

O
One-component (Unary) Phase Diagram
Phase boundaries

❖ For one component system, composition is held constant

❖ Hence, the phase diagram is plotted against the remaining two
variables: Pressure and Temperature
❖ Triple point “O” where all the three phases coexist in equilibrium
 Gibbs’ Phase Rule
❖ Criterion for number of phases that can co-exist within a
system at equilibrium
❖ P+F = C+N
❖ P: number of phases present
❖ F: degrees of freedom
❖ C: number of components comprising the system
❖ N: number of non-compositional variables (temp,
pressure)
Exercise (Gibbs’ Phase Rule)
Exercise (Gibbs’ Phase Rule)
 Exercise (Gibbs’ Phase Rule)

❖ Point in Liquid Phase

 Exercise (Gibbs’ Phase Rule)

❖ Point in Liquid Phase

❖ P =1; C = 1; N = 2
 Exercise (Gibbs’ Phase Rule)

❖ Point in Liquid Phase

❖ P =1; C = 1; N = 2
❖ Hence F = C+2-P = 2.
 Exercise (Gibbs’ Phase Rule)

❖ Point in Liquid Phase

❖ P =1; C = 1; N = 2
❖ Hence F = C+2-P = 2.
❖ F = 2 means, two external variables can be changed without having
to leave the liquid phase region.
Exercise (Gibbs’ Phase Rule)
 Exercise (Gibbs’ Phase Rule)

❖ Point on boiling point line

 Exercise (Gibbs’ Phase Rule)

❖ Point on boiling point line

❖ P = 2, C = 1, N = 2
 Exercise (Gibbs’ Phase Rule)

❖ Point on boiling point line

❖ P = 2, C = 1, N = 2
❖ F = C+2-P=1
 Exercise (Gibbs’ Phase Rule)

❖ Point on boiling point line

❖ P = 2, C = 1, N = 2
❖ F = C+2-P=1
❖ This means that either temperature or pressure can be changed while still
being on the boiling point line; but the other variable is forced to change!
Exercise (Gibbs’ Phase Rule)
 Exercise (Gibbs’ Phase Rule)

❖ At Triple Point
 Exercise (Gibbs’ Phase Rule)

❖ At Triple Point
❖ P = 3, C = 1, N = 2
 Exercise (Gibbs’ Phase Rule)

❖ At Triple Point
❖ P = 3, C = 1, N = 2
❖ F = C+2-P=0
 Exercise (Gibbs’ Phase Rule)

❖ At Triple Point
❖ P = 3, C = 1, N = 2
❖ F = C+2-P=0
❖ This means that no variable can be altered to remain at that state
Solubility Limit and Hume-Rothery’s Rules
❖ Any thermodynamic process that
occurs seeks to minimize its free
energy
❖ Change in free energy is given by
J. W. Gibbs
G= H T S

In a solid, atoms of the solute must fit

(substitutionally or interstitially) so that
change in free energy is non-positive.

Hume-Rothery
 Hume-Rothery’s Rules
1. The greater the difference in size between solute and solvent
atoms, the lower the solubility limit

1.1. 100% solubility limit is possible if the size difference is less

than 8%

1.2. No solubility (0%) for size difference > 15%

2. Greater the difference in electronegativity, lower the
solubility

3. Greater the difference in valence number, lower the solubility

4. 100% solubility is possible only if solvent and solute have
same equilibrium crystal structure
Hume-Rothery’s rules are based
on observations only!

The rules are applicable only for

substitutional solid solutions!
 Binary Phase Diagrams
❖ Variables: Temperature and composition
❖ Pressure is held constant usually at atmospheric pressure
❖ Represent relationships between temperature,
composition and quantities of phase at equilibrium
❖ Microstructure of an alloy is influenced by the above
parameters
❖ Helpful in predicting phase transformations and
resulting microstructures
 Types of Binary Phase Alloys
❖ Completely soluble in liquid state
❖ completely soluble in solid state (Type I, also called isomorphous system)
❖ insoluble in the solid state: the eutectic reaction (Type II)
❖ partly soluble in the solid state: the eutectic reaction (Type III)
❖ formation of a congruent-melting intermediate phase (Type IV)
❖ The peritectic reaction (Type V)
❖ Partly soluble in liquid state: the monotectic reaction (Type VI)
❖ Insoluble in liquid and solid states (Type VII)
❖ Transformations in the solid state
❖ Allotropic change
❖ Order-disorder
❖ The eutecticoid reaction
❖ The peritectoid reaction
 Coordinates of Phase Diagrams
❖ Ordinate: Temperature
❖ Abscissa: Alloy composition in weight percentage or
atomic percent
❖ Conversion from weight percentage to atomic
percentage:
100XA ❖ XA = Weight percentage of
Atomic percent of A = metal A
XA + XB (wA /wB )
100XB (wA /wB ) ❖ XB = Weight percentage of
Atomic percent of B =
XA + XB (wA /wB ) metal B
❖ wA = atomic weight of metal A
❖ wB = atomic weight of metal B
 Type I or Isomorphous system
❖ Substitutional solid phase is formed
❖ Two metals will have same type of crystal structure
❖ Atomic radii differ by less than 8 percent
❖ Cu-Ni system is best example for such system
Ni Cu
Crystal Structure FCC FCC

Atomic radius (nm) 0.1246 0.1278

Electronegativity 1.9 1.8

 Cooling curves to Phase Diagram

http://practicalmaintenance.net/wp-content/uploads/Construction-of-Phase-Diagram-from-Series-of-Cooling-Curves1.jpg

❖ Each cooling curve above is a separate experiment starting from zero time
❖ Pure metals show horizontal line as the phase transformation (solidification)
happens at constant temperature
❖ For a composition 80A-20B, first break is at T1 and second break is at T2 means that
solidification starts at T1 and ends at T2
 Binary Phase Diagram
❖ Region below solidus line is in
solid phase (α)
❖ Region above liquidus line is in
liquid phase
❖ Region between these two lines is
a mixture of solid and liquid
phases
❖ But, the chemical composition and
relative amounts of each phase of
the mixture is not known directly
 Cu-Nickel System
❖ liquid L is homogeneous liquid solution
composed of both copper and nickel
❖ Phase α is a substitutional solid solution of
Cu and Ni atoms and has FCC structure
❖ Below 10850C, Cu and Ni are mutually
soluble in solid state for all compositions
❖ The liquidus and solidus lines intersect at
extremes which are melting points of pure
substances of components in the alloy
❖ Melting of pure Cu and pure Ni happens at
a distinct temperature
❖ For any composition in between, melting
happens over a temperature range
 Interpretation of Phase Diagrams

❖ For a binary system of known composition and

temperature at equilibrium, the information available is
❖ Phases present
❖ Composition of these phases
❖ Percentages or fractions of these phases
 Phases present

❖ Point “A” corresponds to

60%(Ni)-40%(Cu) at 11000C is
in α phase
❖ Point “B” corresponds to 35%
(Ni)-65%(Cu) at 12500C is
having two phases: α and
liquid
 Phase compositions
❖ Locate, temperature-composition point on the
phase diagram
❖ If the point is in single phase region such as
“A”, then the composition of the phase is simply
the overall composition of the alloy: 60%
(Ni)-40%(Cu) in this case.
❖ In case of the point in two phase region such as
“B”
❖ draw a tie line
❖ intersection of the tie line and phase
boundaries on either side
❖ perpendiculars dropped from each
intersection gives the composition of a
particular phase
 Lever Rule
❖ For the two phases present, the sum of their mass fractions must
be unity
❖ WL+Wα = 1
❖ The mass of one of the components (say Ni) that is present in both
the phases (L and α) must be equal to the mass of that component
in the total alloy
❖ CLWL+CαWα = C0
❖ Solving the above two equations leads to lever rule:
❖ WL = (Cα-C0)/(Cα-CL); Wα = (C0-CL)/(Cα-CL)
 Phase amounts
❖ For a single phase, the amount is only one
phase (100%)
liquid
❖ Draw a horizontal line (tie line) at a given tie line
temperature to the boundaries of the field

Temperature
L+α
m n o
❖ At m, the composition is 20B-80A
❖ Draw a vertical line n-n which divides the tie
line in to two parts α
❖ The lengths of the two parts are inversely
A 20 65 80 B
proportional to the amount of phase present
Composition Weight Percentage B
❖ Now use lever rule to find relative amounts
of each phase m n o
20B 80B
❖ WL = (no/mo)*100 = (Co-Cn)/(Co-Cm)
❖ Wα = (mn/mo)*100 = (Cn-Cm)/(Co-Cm)
 Review
❖ A copper-nickel alloy of composition
70wt % Ni - 30 wt % Cu is slowly
heated from a temperature of 13000C
❖ At what temperature does the first
liquid phase form?
❖ What is the composition of liquid
phase?
❖ At what temperature does
complete melting of alloy occur?
❖ What is the composition of the last
solid remaining prior to melting?
Equilibrium Cooling of an Isomorphous alloy

❖ Evolution of microstructure of
Isomorphous alloys during
solidification
❖ Equilibrium Cooling: Phase
equilibrium is maintained at all
points during cooling (very slow
cooling)
❖ Let’s start at 35% Ni at 13000C i.e,
point a
❖ Cooling from this point is nothing
but moving down the vertical line
Equilibrium Cooling of an Isomorphous alloy
❖ At point “a”, alloy is in complete liquid state
with a microstructure shown in figure
❖ Until we reach liquids line no microstructural/
compositional changes
❖ At liquidus, i.e., point “b” (12600C), the first
solid α begins to form with a composition 46%
Ni and 54% Cu denoted as α(46 Ni)
❖ The composition of liquid is still
approximately L(35 Ni)
❖ With further cooling, both compositions and
relative amounts of each phase will change
❖ The fraction of α phase increases with
continued cooling
❖ However, overall composition (35 wt% Ni-65
wt% Cu) will not change
Equilibrium Cooling of an Isomorphous alloy

❖ At 12500C, point “c”, the

composition of liquid and
alpha phases are L(32) and
α(43), respectively
❖ Solidification process is
virtually completed at point
“d” at 12200C, where the liquid
phase has L(24) and α phase
has α(35)
❖ At point “e” the alloy is
completely in α phase
 Non-equilibrium cooling
non-equilibrium cooling line
❖ Assumption: Diffusion in liquid phase is very
high and hence equilibrium exists in liquid state
❖ Cooling starts from a’ L(35%Ni-65%Cu)
❖ First solidification at b’ with solid phase
composition α(46 Ni) and liquid phase
composition L(35 Ni)
❖ Further cooling to c’, composition at solid state
should be α(40 Ni). But, because of low
diffusion rates, gradation in α composition in
solid state
❖ Deviation from equilibrium cooling state
❖ Deviation (dotted line) will be smaller for slow
cooling rates
❖ Distribution of two elements within the grains is
non-uniform - ‘segregation’
 Non-equilibrium cooling
❖ Distribution of two elements within the grins is non-uniform -
‘segregation’
❖ Centre of each grain which is the first part to freeze is rich in high
melting element
❖ Concentration of low melting element increases from the centre to
grain boundary leading to a “cored structure”
❖ Cored structures give rise to inferior mechanical properties
❖ By heating a casting having cored structure, the grain boundary
region melts first which is richer in low-melting element;
❖ Elimination of coring: Homogenization heat treatment just below
solidus line
Mechanical Properties of Isomorphous alloys

❖ Solid solution strengthening

❖ Addition of Ni/Cu leads to increased tensile strength
and decreased ductility
❖ Peaks exist in the graphs
 Variations of Type I

x
http://www.uwgb.edu/dutchs/Graphics-Geol/ROCKMIN/IgnPhaseDiagrams/SOLSOL06.GIF

❖ Possible to have liquidus and solidus line go through a minimum or maximum

❖ Alloy composition at “x” behaves just like a pure metal and it melts/freezes at constant
temperature
❖ Cooling curve will show a horizontal line and such alloys are called “congruent melting
alloys”
❖ The end product of congruent melting alloy is only one phase
❖ Since, alloy “x” has lowest melting point and represents eutectic type, it is sometimes
called “pseudoeutectic alloy”
❖ Examples of alloys with minimum: Cu-Au and Ni-Pd; no known systems with maximum
 Type II alloys
❖ Two metals are completely soluble in liquid state and
completely insoluble in solid state
❖ Strictly speaking, no two metals are completely insoluble in
solid state
❖ In some cases, solubility is so small that they may be
considered insoluble
❖ Raoult’s law: Freezing point of a pure substance will be lowered by
the addition of a second substance if the latter is soluble in the pure
substance when liquid and insoluble when solidified. The amount of
lowering is proportional to molecular weight of the solute
 Cooling curves Type II alloys
❖ The cooling curves for pure metals A and
B show a single horizontal line at their
freezing point
❖ As B is added to A, the temperature for
the beginning of solidification is lowered.
❖ As A is added to B, the temperature for
solidification for those alloys is also
lowered.
❖ Since each metal lowers the freezing
point of the other, the line connecting the
beginning of the solidification called
“liquidus line” should show a minimum
❖ The minimum denoted by “E” at
(40A-60B) is called Eutectic point.
 Cooling curves Type II alloys
❖ The cooling curves for pure metals A and
B show a single horizontal line at their
freezing point
❖ As B is added to A, the temperature for
the beginning of solidification is lowered.
❖ As A is added to B, the temperature for
solidification for those alloys is also
lowered.
❖ Since each metal lowers the freezing
point of the other, the line connecting the
beginning of the solidification called ❖ Eutectic is originated from
“liquidus line” should show a minimum
greek word eutektos which
❖ The minimum denoted by “E” at
(40A-60B) is called Eutectic point.
means easily melting
 Phase Diagram for Type II

• MEN is liquidus line, MFGN is solidus line

• E is eutectic point
• TE is eutectic temperature
• CE (40A-60B) is eutectic composition
Phase Diagram of Type II (Eutectic)
❖ Phase diagram consists of 4 areas
❖ Area above liquidus line (MEN) is a
single phase homogeneous liquid
solution since two metals are completely
soluble in liquid state
❖ Remaining three are 2 phase areas
❖ Phases that exist in two phase area MEN
❖ draw a tie line OL and it touches
liquidus and hence liquid is one
phase
❖ it touches the solidus at “O” and
below the melting point of A and
hence it is solid A
Phase Diagram of Type II (Eutectic)
❖ Phase diagram consists of 4 areas
❖ Area above liquidus line (MEN) is a
single phase homogeneous liquid
solution since two metals are completely
soluble in liquid state
❖ Remaining three are 2 phase areas
❖ Phases that exist in two phase area MEN
❖ draw a tie line OL and it touches
liquidus and hence liquid is one
phase
❖ it touches the solidus at “O” and
below the melting point of A and
hence it is solid A
Phase Diagram of Type II (Eutectic)
❖ Phase diagram consists of 4 areas
❖ Area above liquidus line (MEN) is a
single phase homogeneous liquid
solution since two metals are completely
soluble in liquid state
❖ Remaining three are 2 phase areas
❖ Phases that exist in two phase area MEN
Hypoeutectic
❖ draw a tie line OL and it touches
liquidus and hence liquid is one
phase
❖ it touches the solidus at “O” and
below the melting point of A and
hence it is solid A
Phase Diagram of Type II (Eutectic)
❖ Phase diagram consists of 4 areas
❖ Area above liquidus line (MEN) is a
single phase homogeneous liquid
solution since two metals are completely
soluble in liquid state
❖ Remaining three are 2 phase areas
❖ Phases that exist in two phase area MEN
Hypoeutectic
❖ draw a tie line OL and it touches
liquidus and hence liquid is one
phase
❖ it touches the solidus at “O” and
below the melting point of A and
hence it is solid A
Phase Diagram of Type II (Eutectic)
❖ Phase diagram consists of 4 areas
❖ Area above liquidus line (MEN) is a
single phase homogeneous liquid
solution since two metals are completely
soluble in liquid state
❖ Remaining three are 2 phase areas
❖ Phases that exist in two phase area MEN
Hypoeutectic Hypereutectic
❖ draw a tie line OL and it touches
liquidus and hence liquid is one
phase
❖ it touches the solidus at “O” and
below the melting point of A and
hence it is solid A
Solidification of Alloys of Type II
Alloy 1 (Type II)
❖ Eutectic composition 40A-60B is
cooled from T0
❖ Upto TE it is in liquid phase
❖ At TE this changes to two solid
phases solid A + solid B
❖ Liquid <-> solid A + solid B
eutectic mixture
❖ The above reaction is called eutectic
reaction
❖ Eutectic solidification is
incongruent because of the
difference in composition between
liquid and individual solid phases
Alloy 1 (Type II)
❖ Let’s say at point E, a small portion of
solid A is formed
❖ Liquid gets richer in B
❖ Then, to maintain equilibrium
composition, B gets solidified.
❖ If B is slightly over solidified, then A
gets solidified again
❖ The process continues until complete
solidification into two phases (solid
A+ solid B)
❖ Eutectic mixture is an extremely fine
mixture visible only under
microscope
Alloy 1 (Type II)
❖ The microstructure is a
layered structure with
alternate A and B
❖ The grains grow by adding A
to A and B to B until they
meet another grain
❖ The eutectic solidification is
not congruent because there
is a difference in composition
in liquid and individual solid
phases.
Alloy 2 (Type II)
❖ Alloy 2 is hypoeutectic alloy of composition
80A-20B
❖ Uniform liquid solution until T1
❖ At T1 liquid L1 is saturated in A and as the
temperature is dropped the excess A must
solidify
❖ Liquid will become richer in B by depositing
crystals of A in the above step
❖ Amount of pure solid A increases gradually
by continued precipitation from liquid
❖ At xE remaining liquid would solidify into
fine mixture of A and B
❖ The result is 66.67% pro eutectic A and
33.33% Eutectic mixture
Alloy 3 (Type II)
❖ Alloy 3 is a hypereutectic composition of
10A-90B
❖ It reached liquidus line at T3 and deposits
crystals of solid B unlike Alloy 2 which
deposits crystals of solid A
❖ With decrease in temperature more B will
solidify making liquid richer in A
❖ With further decrease in temperature, amount
of liquid further decreases and reaches a
eutectic composition at TE
❖ At TE, remaining liquid undergoes a eutectic
reaction giving eutectic mixture of solid A and
solid B
❖ After solidification, the alloy will have 75 wt%
of pro eutectic solid B and 25 wt% eutectic
mixture
 Type II Alloy

❖ Eutectic mixture might consist of two solid phases

❖ Two pure solids
❖ Two solid solutions
❖ Two intermediate phases
❖ Any combination of the above
 Type III: Two metals completely soluble in liquid state and partly
soluble in solid state

❖ Most metals are partly

soluble in solid state and
hence this phase diagram
is the most common type
❖ Melting points of two
metals: TA and TB
❖ TAETB: Liquidus line
❖ TAFGTB: Solidus line
❖ Examples: Cu-Ag, Pb-Sn,
Sn-Bi
 Type III Alloys
❖ Single Phase areas
❖ Liquid phase above liquidus
❖ Partially soluble in solid state
implies that a solid solution must
form
❖ Alloys of this type, never solidify
pure A or pure B, but a solid solution
or a mixture of solid solution
❖ The areas below the melting points
of A and B are single phase α and β
solid solutions
❖ α is a solid solution of B in A
❖ β is solid solution of A in B
❖ These solid solution are called
“terminal solid solutions”
 Type III Alloys
❖ Two-Phase areas
❖ liquid+ α
❖ liquid+ β
❖ α+β
❖ At TE, solid solution α dissolves a maximum of
20% B as shown at point F
❖ Similarly, solid solution β dissolves a maximum
of 10% A as shown by point G
❖ With decrease in temperature, the maximum
amount of solute that can dissolve decreases (see
FH and GJ)
❖ FH and GJ are called solvus lines and indicate
the maximum solubility (saturated solution) of B
in A and A in B as a function of temperature
❖ Point E where liquidus lines meet: Eutectic point
Microstructure Evolution in Type III Alloys

❖ Alloys of same base metals but with different

compositions results in different mechanical properties
❖ The microstructure of the alloy is strongly influenced by
the composition of the alloy and the cooling rate during
solidification
❖ We will study the microstructure evolution of 4 alloys in
4 different regions of the phase diagram
 Alloy 1 (Type III)
❖ Alloy 1 is 95A-5B
❖ The solidification of this alloy is
similar to Type I alloys when slowly
cooled
❖ At T1, solidification starts by
formation of crystals of α solid
solution extremely rich in A
❖ With further cooling the liquid as well
as the solid solution gets richer in B
❖ At T4, the remaining liquid would
solidify to α phase and remains the
same down to room temperature
 Alloy 1 (Type III)
❖ Alloy 1 is 95A-5B
❖ The solidification of this alloy is
similar to Type I alloys when slowly
cooled
❖ At T1, solidification starts by
formation of crystals of α solid
solution extremely rich in A
❖ With further cooling the liquid as well
as the solid solution gets richer in B
❖ At T4, the remaining liquid would
solidify to α phase and remains the
same down to room temperature
 Alloy 2(Type III)
❖ Alloy 2 is 30A-70B
❖ This is eutectic composition
❖ Alloy remains liquid until point E which is eutectic
temperature
❖ At point E, liquid undergoes eutectic reaction
forming fine mixture of two solids (solutions) α and
β
❖ The reaction is same as that we have seen in Type II
alloy except that here the liquid transforms to a
mixture of two solid solutions instead of two solids.
❖ The composition of α phase is given by F and β
phase is given by G
❖ With further reduction in temperature, diffusion in
solid state takes place in the two phases resulting in
slight variation of composition due to limited
solubility in solid state
Alloy 3(Type III)
 Alloy 3 (Type III)
❖ Alloy 3 is 60A-40B remains liquid until T3 is reached
❖ The phase changes are similar to the Type II alloy
❖ At T3, the liquid starts to solidify crystals of primary α solid
solution very rich in A
❖ With decrease in temperature, both the liquid and α phase gets
richer in B
❖ When it reaches E, liquid would have eutectic composition and
hence eutectic reaction takes place
❖ After TE, the alloy will have a primary α phase and a eutectic
mixture of α and β phases.
❖ The composition of the α and β phases will be of the compositions
appearing at the ends of the eutectic temperature line (F and G)
❖ With further cooling because of decreased solubility, excess β will
precipitate changing the composition
Alloy 4 (Type III)
Alloy 4 (Type III)

Notice that there is no eutectic mixture

 Alloy 4 (Type III)
❖ Alloy 4 85A-15B remains liquid until T2
❖ This is very interesting case
❖ Initially follows the same process as Alloy 1
❖ Solidification starts at T2 and ends at T5 resulting in
homogeneous single phase α solid solution
❖ At M the solution is unsaturated due to decrease in solubility of
B in A
❖ At N solvus line is hit and the α solution is saturated in B
❖ Further cooling, under slow cooling, the excess B comes out of
solution.
❖ But, B does not come out as pure B as A is soluble in B, it comes
out as β solid solution
❖ At room temperature alloy will have mostly α with small
amount of β
 Alloy 4 (Type III)
❖ Small amount of excess β will be
along grain boundaries
❖ β percent = HP/HJ = 5/85 =
5.88%
❖ If the β phase is relatively brittle,
the alloy will not be very strong
or ductile
❖ Strength of an alloy is determined
by the constituents of the alloy
particularly if the phase is
continuous through out the alloy
❖ Here β phase is continuous along
the grain boundaries
Pb-Sn system
Pb-Sn system
Pb-Sn system
Pb-Sn system

α phase

β phase
Pb-Sn system

α phase

β phase
Pb-Sn system

Why alternating lamellar structure?

α phase

β phase
Pb-Sn system

Why alternating lamellar structure?

α phase Because the atomic diffusion of
lead and tin only need to occur
β phase
over short distances
 Pb-Sn system

Primary or Proeutectic α phase

Eutectic structure of α and β

Properties of Eutectic Alloys Systems
❖ Properties of multiphase alloys depend on
❖ individual characteristics of the phase
❖ distribution of the phases in the microstructure
❖ amount of the phase
❖ number of phases
❖ For many commercially important eutectic systems, one phase is relatively weak
and plastic and other phase is hard and brittle (e.g., Al-Si system)
❖ Strength of alloy increases towards eutectic composition as approached from
plastic side
❖ Beyond eutectic composition the strength decreases due to increase in size and
amount of pro-eutectic brittle phase
❖ These systems, show maximum strength at eutectic composition
 Improved mechanical properties
❖ Two methods for increasing strength and hardness
❖ Cold working
❖ Heat treatment
❖ Most important heat treatment process for non-ferrous metals is
age hardening
❖ Age hardening requires a partial solid solubility
❖ Greater solubility at higher temperature (slope of solves line)
❖ The above two conditions are true for Type III alloys (e.g., Pb-Sn)
 Reading Assignment

❖ Age hardening (6.16 in Avener’s text book)

Type IV - Congruent melting intermediate phase

❖ When one phase changes into another phase

isothermally without any change in chemical
composition, it is called congruent phase change or
congruent transformation
❖ All pure metals solidify congruently
❖ Any intermediate phase may be considered as
another component on phase diagram
❖ Intermediate phase is represented as vertical line if
its has very narrow composition range (e.g.,
intermetallics)
Composition and melting point of pure A, pure B and
a compound AmBn
❖ For example, Mg and Sn form an intermediate
phase
❖ Ni3Al is another intermetallic compound used in
gas turbines for their high temperature strength
Type IV
 Type IV
❖ The phase diagram may be split into two
independent parts, one to show all the
alloys between A and the compound AmBn
and the other to show between AmBn and B
❖ If the compound shows no solubility to
either pure metal and the pure metal
shows some solubility to compound, then
the phase diagram looks as shown
❖ The diagram shows two eutectic mixtures
❖ At T1, Liquid <——> α + AmBn
❖ At T2, Liquid <——> AmBn + β
Type IV
Type V - Peritectic Reaction in incongruent melting intermediate
phase

❖ Peritectic reaction: a liquid and solid react isothermally to

form a new solid on cooling
❖ It is just reverse of Eutectic reaction where a single phase
forms into two new phases on cooling
❖ Liquid + solid1 ———> new solid2 (upon cooling)
❖ Liquid + solid1 <——— new solid2 (upon heating)
❖ The new solid formed is usually an intermediate phase
❖ Some times, the new solid may be a terminal solid solution
Type V - Peritectic Reaction
 Type V - Peritectic Reaction
Alloy 1 Alloy 2 • TADETB: Liquidus line
• TATPGJTETB: Solidus line
T1
Peritectic temperature • TPD: Peritectic reaction
line
• Compound AmBn (70A-30B)
T2 when heated to peritectic
temperature (at G),
F H decomposes into two
phases: liquid solution and
K solid A
• The above is an example of
incongruent-melting
intermediate alloy
• Ag-Pt system is a good
example of formation
terminal solid solutions
through peritectic reaction
 Type V - Peritectic Reaction
Alloy 1 Alloy 2 • TADETB: Liquidus line
• TATPGJTETB: Solidus line
T1
Peritectic temperature • TPD: Peritectic reaction
line
• Compound AmBn (70A-30B)
T2 when heated to peritectic
temperature (at G),
F H decomposes into two
phases: liquid solution and
K solid A
• The above is an example of
incongruent-melting
intermediate alloy
• Ag-Pt system is a good
example of formation
terminal solid solutions
through peritectic reaction
 Alloy 1 (Type V)
Alloy 1 Alloy 2
❖ Alloy I (90A-10B) starts
solidifying at T1 (Liquid +
T1
Peritectic temperature
pure solid A)

❖ Composition just above TP is

T2 L(60A-40B) and solid(100A)

F H
❖ Relative amounts just above
F: Solid:FD/TPD = 75%and
liquid: TPF/TPD=25%
K
❖ What happens just after F?

❖ Does all the liquid gets

converted into AmBn?

❖ Theoretically it’s not possible

as AmBn has 70% A while
liquid at F has only 60%A.
 Alloy 1 (Type V)
❖ The conditions just below peritectic temperature
❖ AmBn has a composition of (70A-30B) with a relative amount
of (TPF/TPG =) 33% in the A+AmBn mixture
❖ Hence, the liquid should react with the right amount of solid
A, in this case 8% to bring its composition to that of AmBn
❖ (60A/25%)Liquid + (100A/8%) solid ———> (70A/
33%)AmBn
❖ Above reaction happens all around the the surface of each
grain of solid A and when the correct composition is reached,
liquid gets solidified into AmBn
❖ Further reaction is slow (diffusion!) and when it is
completed, all the liquid will be consumed and 67% of A will
be left
❖ Final microstructure will have grains of primary A
surrounded by the compound AmBn
Alloy 2 (Type V)
 Alloy 2 (Type V)
❖ Alloy 2 is 65A-35B and at T2 solidification (of
pure A) starts
❖ With further cooling, liquid gets richer in B
❖ At H, liquid composition is 60A-40B and it has
35/40 = 87.5% of liquid and 12.5% solid A
❖ GD is not part of the solidus line and hence after
the peritectic reaction (L+S1->S2), some liquid
must remain
❖ Hence, all solid A must transform into AmBn
❖ 60A (Liquid)+100A(Solid) ——> 70A(AmBn)
❖ Amount of liquid entering the reaction GH/GD
= 50%
❖ Hence, 37.5% liquid would have reacted with
12.5% solid A to give 50% of the compound AmBn
 Alloy 2 (Type V)
❖ With further cooling, liquid
separates crystals of AmBn
❖ Liquid gets richer in B
❖ When it hits Eutectic temperature,
the liquid percentage is (5/50)*100 =
10%
❖ The 10% liquid would transform to
a Eutectic mixture of AmBn+B which
is 10%
❖ Remaining 90% would be
Proeutectic AmBn
Phase Diagrams with Intermediate Phases
 Type VI

❖ Two liquids partly soluble in liquid state

❖ The Monotectic reaction
❖ When one liquid forms another liquid plus a solid on
cooling is called Monotectic reaction
 Type VI: Two liquids partly soluble in liquid state
❖ Monotectic reaction: L1—(cooling)——>L2+Solid
❖ Liquidus line: TACFETB
❖ Solidu line: TATEJTB
❖ Alloys between point C and F and above
TM will contain two liquid solutions L1 and
L2
❖ CD and FG shows the composition of
liquid phases in equilibrium at high
temperatures
❖ CD and FG are dotted lines because their
exact location is not known
❖ From the form of CD and FG, at high
temperatures, again only one liquid
solution exists where CD and FG could
meet
 Alloy x (Type VI)
❖ L1 is the liquid solution of B dissolved in
A
❖ L2 is the liquid solution of A dissolved in
B
❖ Alloy x: 90A-10B is a single phase liquid
solution (L1) until x1
❖ Solidification starts by forming crystals of
pure metal A and liquid gets richer in B
❖ At monotectic temperature TM at x2,
liquid composition is 80A-20B
❖ Below the line (TM) two phases are
present A and L2
❖ Does all L1 above TM gets converted to
L2? (No, check the relative amounts)
 Alloy x (Type VI)
❖ Composition of L2 is given by point F, i.e.,
40A-60B whereas L1 id 80A-20B
❖ Hence, L2 could not have have formed by
L1 itself
❖ Furthermore, L1 is rich in A and L2 is rich in
B
❖ There is too much A in L1
❖ Hence, at the horizontal line TM, sufficient
solid A is precipitated from L1 to bring its
composition to the right amount to form L2
❖ Above the line solid A is 50% and L1 is 50%
❖ Below the line, L2 is (10/60) 17% and solid
A is 83%
❖ Therefore at the monotectic line 50% of L1
must have formed 17% L2 and 33% solid A
 Alloy x (Type VI)
❖ Point C is monotectic point
❖ Alloys left to point C are called
hypomonotectic alloys
❖ Alloys to the right of point C and upto
F are called hypermonotectic alloys
❖ After the monotectic reaction, with
further cooling, more solid A will form
from L2
❖ At Eutectic point (x3), remaining L2 will
form a fine eutectic mixture of solid A
plus solid β
❖ The fine microstructure will consist of
(70/80)87.5% solid A and (10/80)12.5%
of eutectic mixture of A+ β
 Alloy y (Type VI)
❖ Alloy y: 70A-30B
❖ Occurrence of two liquids in
hypermonotectic alloys (alloys
between C and F)
❖ The liquids will separate into two
layers according to density (if
given sufficient time)
❖ Also, it is possible to have two
liquids existing as emulsions
(droplets of one liquid surrounded
by other) : Not observed in metals
 Alloy y (Type VI)
❖ At high temperature, this alloy exists as single
liquid solution L1
❖ With cooling, limit of liquid miscibility is
encountered at y1 and the second liquid
solution L2 appears
❖ Composition of L2 may be obtained by drawing
a tie line and lever rule
❖ With further cooling, monotectic point is
encountered where L2 composition is 40A-60B
which is monotectic composition which is
(10/40) 25% of the total L1+L2
❖ The L1 portion now reacts according to
monotectic reaction to form more of L2+solid A
❖ With further cooling more of solid A is formed
from L2 and finally reaching Eutectic point
where the remaining L2 (37.5%) converts into a
fine eutectic mixture of solid A and solid β
Example: Cu-Pb system (Type VI)
 Type VII
❖ Two metals insoluble in liquid and solid states (e.g: Al-
Pb)
❖ If point C and F of (Type VI) are moved in
opposite directions, then we achieve type VII as
shown here
❖ Many combinations of metals showing complete
insolubility
❖ When cooled, two metals starts to solidify at
their individual freezing temperature forming
two distinct layers with sharp interface and
with no diffusion
❖ Limiting case of monotectic point (upper
horizontal line)
❖ Limiting case of eutectic reaction (lower
horizontal line)
 Transformations in Solid State

❖ Allotropy
❖ Order-disorder transformation
❖ Eutectoid Reaction
❖ Peritectoid Reaction
 Allotropy
❖ Several metals exist in more than one type of
crystal structure depending on temperature
❖ Examples: Iron, tin, cobalt and manganese
❖ On equilibrium diagram, allotropic change
is represented by a point or points on the
vertical line which represents the pure metal
❖ In the figure (side) 𝜸 solid solution field is
looped
❖ Pure metal A and alloys rich in A undergo
two transformations
❖ Fe-Si, Fe-Mo and Fe-Cr show this looped
solid solution field Hypothetical phase diagram of metal A
❖ Since the type of iron in this temperature undergoing two allotropic changes
range is 𝜸 iron, the field is called 𝜸 loop.
Order-disorder transformation
 Order-disorder transformation
❖ The solute atoms in a substitutional solid
solution do not occupy any specific position
and hence it is called disordered solid solution
❖ If the (some of them) random solid solutions
are cooled slowly, they undergo rearrangement
of atoms where the solute atoms move into
definite positions in the lattice forming
ordered solid solutions
❖ Ordering is most common in isomorphous
alloys
❖ On the phase diagrams, ordered solutions are
designated as α’, α’’, . etc. or α’, β’, etc.
❖ The area in which they are found is generally
bounded by a dash-dot line
 Order-disorder transformation
❖ If the ordered phase has the same
lattice structure as disordered
phase, the effect on mechanical
properties is negligible
❖ With ordering, a significant
reduction in electrical resistance
may be possible
❖ Observe the sharp drop in electrical
resistivity at the compositions
which correspond to ordered
phases of AuCu3 and AuCu
 Eutectoid Reaction
❖ A common reaction in solid state
❖ A solid phase transforms into two new solid
phases
❖ The resultant eutectoid mixture is extremely fine
just like eutectic mixture
❖ Difficult to find if the mixture is from eutectic
reaction or eutectoid reaction under microscope
❖ Liquidus: TAETB
❖ Solidus: TAFGTB
❖ Eutectic mixture is composed of phases that occur
at both ends of eutectic temperature line (𝜸 solid
solution and β solid solution)
❖ Point M indicates an allotropic change for the pure
metal A
❖ N is Eutectoid point
 Eutectoid Reaction

❖ Reading Assignment for

further details
 Peritectoid reaction

❖ Also a common reaction in

solid state
❖ The new phase is usually an
intermediate alloy or
sometimes a solid solution
❖ EF is the peritectoid
temperature line
Equilibrium Diagram Reactions
Iron-Iron Carbide Equilibrium Diagram
Cooling Curve of pure iron

1538

1394

910
765

source: http://steelandcolor.bplaced.net/Technology-Tools.html
Iron-Carbon Equilibrium Diagram

A Portion of Fe-C equilibrium diagram

Iron-Iron Carbide Equilibrium Diagram
Iron-Iron Carbide Equilibrium Diagram

Eutectic point
Iron-Iron Carbide Equilibrium Diagram

Eutectic point

Eutectictoid
Iron-Iron Carbide Equilibrium Diagram
Peritectic point

Eutectic point

Eutectictoid
 Iron-Iron Carbide Equilibrium Diagram
❖ Fe-Fe3C diagram is not a true equilibrium
diagram
❖ Equilibrium implies that the phases do not
change with time
❖ However, Fe3C decomposes to iron and
carbon (graphite)
❖ But, this decomposition takes extremely long
time; for instance at 1300 F, it takes several
years to form graphite
❖ Hence, for practical purposes, it can be
considered as equilibrium diagram
❖ This is iron-iron carbide equilibrium digram;
not iron-carbon equilibrium diagram
Fe-Fe3C Equilibrium diagram
 Fe-Fe3C Equilibrium Diagram
❖ Pure iron upon heating
experiences two crystal structure
changes
❖ At room temperature, the stable
form called ferrite or α-iron, has
BCC structure
❖ Ferrite changes to FCC austenite,
or γ-iron at 1666F (912C)
❖ Austenite persists upto 2554F
(1394C) at which FCC austenite
reverts back to BCC phase known
as δ-ferrite which finally melts at
2800F (1538C)
 Delta Region of Fe-Fe3C Equilibrium Diagram
❖ Portion of the diagram in the
upper left hand corner
❖ This region is called “delta-region”
❖ Line MB (2720 F) is peritectic
reaction line
❖ P is the peritectic point at 0.18% C

❖ Liquid+δ —-cooling—> γ (austenite)

❖ Maximum solubility of carbon in BCC δ Fe is 0.1% (point M) while in FCC γ Fe, the
solubility is much higher (point C).
❖ Presence of carbon influences the allotropic change δ γ

❖ The temperature for allotropic change increases with increase in C content (line NM)
 Delta Region of Fe-Fe3C Equilibrium Diagram
❖ Significance of line NMPB
❖ On cooling, line NM represents the
beginning of allotropic change from
bcc δ Fe to fcc γ Fe for alloys less than
0.1% C
❖ MP represents the beginning of
allotropic change through peritectic
reaction for alloys between 0.1% C
and 0.18%C
❖ NP - end of allotropic change ❖ Alloys with more than 0.5% C solidify to
❖ PB - beginning and end of allotropic austenite directly (no allotropic change or
change by peritectic reaction for delta solid solution or peritectic reaction)
alloys between 0.18%C and 0.5%C ❖ The delta region is of no engineering
❖ At PB allotropic change happens at interest as the phase is unstable at room
constant temperature temperature
 Fe-Fe3C Equilibrium Diagram
❖ Eutectic point: E at 4.3%C and 2065F (1147 C)
❖ Eutectoid point: J at 0.8% C and 1333F (727 C)
❖ CED: Eutectic line where liquid iron
transforms to a eutectic mixture of austenite
(γ-iron) and cementite (Fe3C); the mixture is
called ledeburite
❖ The above eutectic mixture is not seen in the
microstructure. Why?
❖ Austenite is not stable at room
temperature
❖ Small solid solution area left to line GH: at
1666 F (912 C), change of crystal structure of
pure iron from FCC gamma to BCC alpha.
❖ The above area is portion of small amount of
carbon dissolved in bcc alpha iron called
ferrite
 Fe-Fe3C Equilibrium Diagram
❖ HJK: Eutectoid line where austenite
transforms to a eutectoid mixture of ferrite
and cemenitite called pearlite
❖ Pearlitic steels are used in drawing ropes:
piano strings, suspension bridges, steel cords
for tyre reinforcement etc.
❖ Pearlite is one of the strongest structural bulk
material on earth!
❖ Any austenite present in the solution should
transform to eutectoid mixture of ferrite and
cementite
❖ Below eutectoid temperature line every alloy
will consist of a mixture of ferrite and
cementite
❖ Steels - less than 2% C
❖ 2%C < Cast iron < 6.67%C
Cooling of a Eutectoid iron-carbon alloy
❖ Cooling of an alloy with eutectoid
composition (0.8% Carbon)
❖ At a the microstructure has gamma
phase (Austenite)
❖ At 727 C, the gamma phase
undergoes an allotropic
transformation due to eutectoid
reaction line and transforms to fine
microstructure of alpha iron(ferrite) 0.8% C
and Fe3C (Cementite)
❖ The fine microstructure is called
pearlite
Cooling of a Eutectoid iron-carbon alloy

❖ gamma (0.8 wt % C) —> ferrite

(0.025 wt%C)+Cementite (6.7 wt
%C)
❖ The relative layer thickness of ferrite
(alpha) iron and cementite (Fe3C) in
pearlite is 8 to 1
Microstructure of eutectoid steel showing Pearlite
consisting of alternate layers of alpha ferrite (light)
❖ Mechanically Pearlite has properties and cementite (thin dark)
between soft ductile ferrite and hard
brittle cementite
❖ The phase transformation requires a
redistribution of carbon by diffusion
 Hypoeutectoid alloy
❖ Let us go through cooling of a
hypoeutectoid alloy (C0 ~ 0.3% C)
❖ At c the alloy has gamma (austenite)
phase and until it touches the line MO
nothing happens micro structurally
❖ At point d, the system is in two phase
region (alpha and gamma)
❖ Most alpha particles form along the grain
boundaries of gamma
❖ Composition of alpha and gamma phases
is determined by tie line
❖ At d, alpha consists of 0.02% C and
gamma consists of 0.4% C
 Hypoeutectoid alloy
❖ With further cooling, weight percentage of
alpha is increasing and gamma is
decreasing as can be seen by drawing a tie
line
❖ The alpha phase gets slightly richer in C
along MN while the change in
composition of gamma is more along MO
❖ Cooling from d to e results in increased
fraction of alpha phase
❖ At this point alpha phase has 0.025% C
and gamma phase has 0.8% C
❖ With further cooling just below eutectoid
line, at f, all the gamma phase would
transform to pearlite
Hypoeutectoid Alloy

Microstructure of a 0.38 wt% C

 Hypoeutectoid alloy
❖ There is virtually no change in already formed ferrite
❖ The eutectoid reaction results in transformation of ~ 37% [(0.3-0.025)/0.8)]
gamma phase to fine eutectoid mixture of ferrite and cementite called
“pearlite”
❖ At the eutectoid line, austenite is an interstitial solid solution with each
grain dissolving 0.8% C in FCC Fe
❖ Ferrite however is BCC iron dissolving very little C
❖ So, change in crystal structure can not occur until the additional carbon
comes out of solution
❖ So, the first step is precipitation of carbon atoms to form plates of cementite.
❖ In the area next to cementite the iron is depleted of C and hence they can
form BCC alpha iron (ferrite) immediately
 Hyper eutectoid alloy
❖ Cooling of a hypereutectoid alloy at C1 (~1.1)
wt % C
❖ At g, the alloy is in single phase FCC gamma
iron (austenite)
❖ When it touches the line PO it enters a two
phase region (gamma-Fe3C).
❖ Just below PO, at h, particles of Fe3C start
appearing along the gamma grain boundaries
❖ Line PO indicate the maximum amount of C
solubility
❖ The solubility of C at h is lower than at g
❖ The excess C comes out of gamma and forms
as cementite along gamma grain boundaries
 Hyper eutectoid alloy
❖ Just above point i, cementite is (1.1-0.8)/
(6.7-0.8) = 5.08% and remaining is gamma
phase
❖ When it hits the eutectoid line remaining
gamma iron would undergo a eutectoid
reaction forming pearlite
❖ At the eutectoid line all the (~95%) gamma
phase undergoes an allotropic change of fcc
austenite to bcc ferrite
❖ As in the case of hypoeutectoid alloys,
remaining cementite (having 0.8% C) would
form a lamellar eutectoid mixture of pearlite
❖ Line PO involves only a change of carbon
solubility whereas the horizontal line involves
allotropic change
Hyper eutectoid alloy

Microstructure of a 1.4% wt% C

Micro structural differences in hypo and hypereutectoid alloys
Effect on Mechanical Properties
 Effect on Mechanical Properties
❖ Ferrite is soft and has medium tensile strength (40000 psi)
❖ Cementite is hard with low tensile strength (5000 psi)
❖ Combination of these two phases in eutectoid composition as pearlite
produce an alloy with much higher tensile strength (120,000 psi)
❖ Amount of pearlite increases with increase in C percentage for hypoeutectoid
steels
❖ Hence, tensile strength and Brinell hardness increases up to eutectoid
composition (0.8% Carbon)
❖ Ductility and impact strength decreases with increase in carbon content
❖ Beyond eutectoid composition strength levels off or sometimes show a
decrease due to brittle cementite network
❖ BHN continues to increase due to hard cementite network
 Classification of Steels
❖ Method of Manufacture
❖ Bessemer Steel, Open Hearth Steel, Electric Furnace Steel, Crucible
Steel
❖ Use
❖ Machine Steel, Spring Steel, Boiler Steel, Structural Steel and Tool
Steel
❖ Chemical Composition
❖ By percentage of alloying elements
❖ This is the most popular classification
SAE Steel Grades by Chemical Composition
❖ Steels are designated by a four or five digit
number system which represents the ❖ For alloy steels, second digit
approximate content of the important indicates approximate percentage of
alloying elements
predominant alloying element
❖ First digit indicates type of steel
❖ Last two or three digits indicate the
❖ 1 - Carbon Steel
mean carbon content divided by 100.
❖ 2 - Nickel Steel
❖ 3 - Nickel-Chromium Steel
❖ 2520 indicates a nickel steel of
❖ 4 - Molybdenum Steel
approximately 5 percent Nickel and
0.2% Carbon
❖ 5 - Chromium Steel
❖ 6 - Chromium-Vanadium Steel ❖ In addition to the number, AISI
❖ 7 - Tungsten Steel specifications may include a letter
prefix to indicate the manufacturing
❖ 8 - Nickel-Chromium-Molybdenum Steel
process employed in producing steel
❖ 9 - Silicon-Manganese Steel
 Classification by Carbon Content

❖ Low Carbon Steels: up to 0.25% C

❖ Medium Carbon Steels: 0.25%C - 0.55%C
❖ High Carbon Steels - 0.55%C - 2%C
❖ In all the steels certain amount of Manganese is present
to improve hardenability
 Effect of other alloying elements
❖ Sulphur
❖ Generally below 0.05%
❖ Sulphur combines with iron to form iron sulfide (FeS) which intern forms a low
melting point eutectic alloy
❖ The FeS phase is concentrated around grain boundaries
❖ Steel becomes brittle due to melting of iron sulphide destroying the cohesion
between the grains when forged or rolled at high temperatures
❖ In the presence of Manganese, it forms MnS rather than FeS
❖ MnS pass out as slag or remain as a well-distributed inclusion throughout the
structure
❖ For free machining steels, sulfur is 0.08-0.35% which improves the
machinability due to presence of more numerous sulphur inclusions leading to
break-up of chips
 Effect of other alloying elements
❖ Manganese
❖ Manganese is present in all commercial plain carbon steels in
the range of 0.03 to 1%
❖ Manganese counters the ill effects of sulfur by forming
manganese sulphide
❖ If more manganese is present, then it forms a compound with
carbon as Mn3C associated with Cementite (Fe3C)
❖ It also acts as a deoxidising agent improving the soundness of
castings
❖ Steel is called an alloy steel if Mn content is more than 0.8%
 Effect of other alloying elements
❖ Phosphorous
❖ Phosphorous content is generally kept below 0.04%
❖ This small quantity tend to dissolve in ferrite increasing
the strength and hardness slightly
❖ In some steels 0.07 to 0.12% phosphorous seems to
improve cutting properties
❖ In large quantities, phosphorous reduces ductility
leading to cracking of steel when cold worked making it
cold-short
 Effect of other alloying elements

❖ Silicon
❖ Silicon content in commercial steels is in the range of
0.05 to 0.3%
❖ Silicon dissolves in ferrite, increasing the strength of
the steel greatly while decreasing the ductility
❖ It promotes deoxidation of molten steel through
formation of SiO2, thus leading to sound castings
 References
❖ Sidney H Avener, Introduction to Physical Metallurgy, Tata
McGrawHill, Second Edition, (2010)
❖ William D Callister Jr. and David G. Rethwisch
Materials Science and Engineering: An Introduction, John
Wiley, 8th Edition, (2009)
❖ Reza Abbaschian, Lara Abbaschian and Robert E. Reed-
Hilll, Physical Metallurgy Principles, CENGAGE
Learning, 4th edition, (2009)