MODULE 02

PHASE DIAGRAM
SOLUBILITY LIMIT

• 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.
• The addition of solute in excess of this solubility limit results in the formation of
another solid solution or compound that has a distinctly different composition.
• Solubility limit increases with temperature.

• is generally represented as a solid line in the phase diagram.

SOLUTE
The solute is the substance that is dissolved in a solvent, often present in a smaller
amount than the solvent.
SOLVENT
The solvent is the substance in which the solute dissolves, typically present in a
larger amount than the solute and often determines the solution's physical state
(solid, liquid, or gas).
SOLUTION
A solution is a homogeneous mixture formed when a solute dissolves in a solvent.
SOLID SOLUTIONS
Most of the alloys are formed as solid solutions. Like liquid solution, solid solution also
contains a solute and solvent. A solidified alloy with a single crystal structure containing 2 or
more types of atoms in the unit cell is called a solid solution.
Solid solutions are of 2 types (1) substitutional and (2) interstitial
1) Substitutional solid solution
In this solid solution there is a direct substitution of one type of atom for another. In a Cu-Ni
solid solution, solute atoms (Ni) takes the positions normally occupied by solvent (Cu) atoms.
When solute atoms are substituted randomly, it is called random (disordered) solid solution.
When solute and solvent atoms are arranged in a regular fashion, it is termed as an ordered
substitutional solid solution.
2) Interstitial Solid solution
When solute atoms are much smaller than solvent atoms, they can occupy interstitial
positions between solvent atoms. C,H, N and B atoms are very small and can form interstitial
solid solutions. An example is steel containing carbon in iron.
In some cases, substitutional and interstitial solid solutions can coexist. Example is Cr-Ni steel
containing interstitial carbon atoms with Cr and Ni in substitutional positions.

HUME ROTHERY'S RULES

• Hume-Rothery proposed 4 conditions for forming substitutional solid solutions. These
are known as Hume-Rothery's Rules.
1) Size factor: Size difference between solvent and solute atoms must be less than 15%. For
extensive solid solubility, size difference should be within 8%.
2) Crystal structure factor: The crystal structures of solvent and solute atoms must be same.
3) Electro negativity factor: Difference in electro-negativity of solvent and solute must be
small.
4) Valency factor: In general a metal has a tendency to dissolve a metal of higher valency.
Hence a solvent must have a lower valency than solute.
For example:-
Solid solution of Cu and Ni is an example. These elements form solid solutions at all
proportions. They are completely soluble in each other in solid and liquid states. If we apply
Hume-Rothery's rules:
1. Atom diameters of Cu and Ni are 0.128 and 0.125 nm respectively (apprx 2.5% difference).
2. Both have FCC crystal structure.
3. Electro-negativity values are 1.9 and 1.8 respectively.
4. Valency of Cu is 1 and valency of Ni is 2.

• For interstitial solid solution, Hume-Rothery's rules are:

1. Solute atoms must be smaller than the voids in the solvent lattice
2. Solute and solvent should have similar electro-negativity.

PHASE
• A phase may be defined as a homogeneous portion of a system that has uniform
physical and chemical characteristics. Every pure material is considered to be a phase;
so also is every solid, liquid and gaseous solution.
• If more than one phase is present in a given system, each will have its own distinct
properties and a boundary separating the phases will exist
• Also, when a substance can exist in two or more polymorphic forms (e.g., having both
FCC and BCC structures), each of these structures is a separate phase because their
respective physical characteristics differ.
• A single-phase system is termed homogeneous.
• Systems composed of two or more phases are termed mixtures or heterogeneous
systems. Most metallic alloys and, for that matter, ceramic, polymeric, and composite
systems are heterogeneous.

PHASE EQUILIBRIUM
• Equilibrium is described in terms of a thermodynamic quantity called the free energy.
In brief, free energy is a function of the internal energy of a system and also the
randomness or disorder of the atoms or molecules (or entropy).
• A system is at equilibrium if its free energy is at a minimum under some specified
combination of temperature, pressure, and composition.

• Phase equilibrium is applicable for materials with more than one phase.
 • The microstructure of a material attains stability when the it reaches equilibrium. (i.e,
the number of phases, their concentration and their relative distribution becomes
constant).

METASTABLE STATE
• It is the state achieved by a system before it reaches the final equilibrium state.
• A material need time to change its microstructure to a equilibrium state. When this
required time is too large, it is of less importance and we use the metastable state
achieved in between for our engineering application.
• A phase diagram shows only equilibrium states, but not the time required to achieve
those equilibrium states.

difference between the states of phase equilibrium

and metastability

THE GIBBS PHASE RULE

• This rule represents a criterion for the number of phases that coexist within a system
at equilibrium and is expressed by the simple equation.

• P is the number of phases present. The parameter F is termed the number of degrees
of freedom or the number of externally controlled variables (e.g., temperature,
pressure, composition) that must be specified to define the state of the system
 completely. The parameter C represents the number of components in the system.
Components are normally elements or stable compounds. N is the number of non
compositional variables (e.g. temperature and pressure).

• Let us demonstrate the phase rule by applying it to binary temperature–composition

phase diagrams, specifically the copper–silver system, Figure 9.7. Because pressure is
constant (1 atm), the parameter N is 1—temperature is the only non compositional
variable.
P+F=C+1
The number of components C is 2 (namely, Cu and Ag), and
P+F=2+1=3
F=3−P
Consider the case of single-phase fields on the phase diagram (e.g., , , and liquid
regions). Because only one phase is present, P = 1 and
F=3−P
=3−1=2
This means that to completely describe the characteristics of any alloy that exists
within one of these phase fields, we must specify two parameters—composition and
temperature, which locate, respectively, the horizontal and vertical positions of the
alloy on the phase diagram.

Thus, it is necessary to specify either temperature or the composition of one of the

phases to completely define the system.

For binary systems, when three phases are present, there are no degrees of freedom
because
F=3–P
= 3-3=0
This means that the compositions of all three phases—as well as the temperature—
are fixed.
Q) For a ternary system, three components are present; temperature is also a variable. What
is the maximum number of phases that may be present for a ternary system, assuming that
pressure is held constant
Ans: F=C−P+2 where:
F is the number of degrees of freedom (independent variables that can be varied),C is the
number of components, P is the number of phases.
For a ternary system C=3) with constant pressure (P and T are the only variables), the phase
rule simplifies to:𝐹=3−𝑃+1
For the maximum number of phases, we set
F=0 (no degrees of freedom, meaning the system is completely constrained):
0=3−𝑃+1
P=4
Thus, the maximum number of phases that may be present in a ternary system at constant
pressure is 4.

Alloys
Limitations of Pure Metals and Need of Alloying
Pure metals have the following limitations:
1. Poor properties: Generally pure metals are not strong enough for engineering applications
where stresses have to be withstood. Combination of low strength with high ductility results
in easy plastic deformation and consequent change in size and shape. This makes the
component useless.
2. High cost: Pure metals are very costly because of the need for extensive refining steps.
3. Lack of availability (scarcity)
These limitations are overcome by alloying. Pure metals are mixed or alloyed with other
metals to form alloys. Yield strength, tensile strength, hardness and creep resistance of pure
metals are improved by alloying. At the same time, ductility and electrical conductivity are
reduced. For example, pure silver can be made stronger and harder when some copper is
added to it which also reduces the cost.

Classification of Alloys
Almost all metallic materials in use today are in the form of alloys. These are formed by
melting two or more metals together. Alloys can be classified into three types namely solid
solution alloy, multi-phase alloy and inter-metallic compound.

• If X and Y are two component metals, solid solution will form if the strength of X-Y
bond is intermediate between strengths of X-X and Y-Y bonds. Solid solution has a
single crystal structure .In the unit cell, both metal atoms are present. An example is
Cu-Ni system
• A multi phase mixture is formed if X-Y bond is weaker than X-X and Y-Y bonds. The
liquid alloy solidifies into two distinct and separate phases. One phase will be richer in
X and the other richer in Y. Sn-Pb alloy is an example.
 • An inter-metallic compound is formed when X-Y bond is stronger than X-X and Y-Y
bonds. An example is Fe3C in iron-carbon system.
It is not true that alloys solidify in the same manner at all compositions. In some alloy
systems, components are completely soluble in each other in solid state. In these alloys, solid
solutions are formed at all compositions. In some alloy systems, the components are partially
soluble in solid state. In this case, solid solutions are formed at some compositions and phase
mixtures at other compositions. If the components are completely insoluble in solid state,
phase mixtures are formed at all compositions. In some alloy systems inter-metallic
compounds are formed at certain compositions with solid solutions or phase mixtures.

Types of Phase diagrams

ONE-COMPONENT (OR UNARY) PHASE DIAGRAMS
• Three externally controllable parameters affect phase structure -temperature,
pressure, and composition—and phase diagrams are constructed when various
combinations of these parameters are plotted against one another.
• one-component system, in which composition is held constant (i.e., the phase
diagram is for a pure substance); this means that 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).

Most often, the pressure axis is scaled logarithmically.

Explanation
❖ The three curves shown on the plot (labeled aO, bO, and cO) are phase boundaries; at
any point on one of these curves, the two phases on either side of the curve are in
equilibrium(or coexist) with one another.
❖ Equilibrium between solid and vapour phases is along curve aO. Equilibrium between
the solid–liquid boundary, curve bO. Equilibrium between the liquid–vapor boundary
,curve cO.
 ❖ Upon crossing a boundary (as temperature and/or pressure is altered), one phase
transforms into another.
❖ For example, at 1 atm pressure, during heating the solid phase transforms to the
liquid phase (i.e., melting occurs) at the point labelled 2 (i.e. ,the intersection of the
dashed horizontal line with the solid–liquid phase boundary); this point corresponds
to a temperature of 0°C. The reverse transformation (liquid-to-solid, or solidification)
takes place at the same point upon cooling.
❖ Similarly, at the intersection of the dashed line with the liquid–vapor phase boundary
(point 3 at 100°C) the liquid transforms into the vapor phase (or vaporizes) upon
heating; condensation occurs for cooling. Finally, solid ice sublimes or vaporizes upon
crossing the curve labelled aO.
❖ All three of the phase boundary curves intersect at a common point, which is labelled
O. This means that at this point only, all of the solid, liquid, and vapor phases are
simultaneously in equilibrium with one another. Appropriately, this, and any other
point on a P–T phase diagram where three phases are in equilibrium, is called a triple
point; sometimes it is also termed an invariant point in as much as its position is
distinct, or fixed by definite values of pressure and temperature. Any deviation from
this point by a change of temperature and/or pressure will cause at least one of the
phases to disappear.

BINARY PHASE DIAGRAMS

❖ Binary phase diagrams are maps that represent the relationships between
temperature and the compositions and quantities of phases at equilibrium, which
influence the microstructure of an alloy.
❖ Many microstructures develop from phase transformations, the changes that
occur when the temperature is altered (typically upon cooling). This may involve
the transition from one phase to another or the appearance or disappearance of a
phase.
❖ Binary phase diagrams are helpful in predicting phase transformations and the
resulting microstructures, which may have equilibrium or nonequilibrium
character.

Types of Binary Phase Diagrams

1) ISOMORPHOUS SYSTEMS
➢ A binary (two-component) system where the components are completely soluble
in both the liquid and solid states, forming a single solid solution phase.
Three different phase regions exist; liquid (L), solid(a) and Lea phase. Boundary between Land
L+ a is called liquidus curve. The boundary between Lea and 5 is solidus curve. 3 kinds of
information are available from phase diagram viz. (i) phases present (ii) composition of phases
and (iii) relative percentage of the phases.

(i) Phases present

Let us select a point X. This alloy contains 60% Ni and the temperature is 1150 deg * C This
point is within a (solid) region. Hence there is only a phase Consider point Y, an alloy of 35%
Ni and temperature is 1250 ^ 6 * C This point contains 2 phases; L and a, at equilibrium.

(ii) Composition of Phases

When there is only one phase, composition of the phase is same as that of the alloy. E.g.
Point X has only one phase; composition is 60% Ni. When 2 phases are present, composition
of each phase is determined by tie line method as given below.
Step1. A tie line is drawn horizontally touching the point and parallel to X axis.
Step2. Intersections of the line with phase boundaries at the 2 sides are noted.
Step3. Vertical lines are drawn downwards from the two intersecting points. Composition of
each phase is noted from X axis.
E.g. Point Y is in 2 phase region. Horizontal line is drawn at Point Y. Verticals are drawn from
the intersections. We find that a phase contains 42.5% Ni whereas liquid phase contains
31.5% Ni.

(iii) Amount of Phases

If the composition and temperature position is located within a two-phase region, things are
more complex. The tie line must be used in conjunction with a procedure that is often called
the lever rule (or the inverse lever rule), which is applied as follows:
1. The tie line is constructed across the two-phase region at the temperature of the alloy.
2. The overall alloy composition is located on the tie line.
3. The fraction of one phase is computed by taking the length of tie line from the overall alloy
composition to the phase boundary for the other phase and dividing by the total tie line
length.
4. The fraction of the other phase is determined in the same manner.
5. If phase percentages are desired, each phase fraction is multiplied by 100. When the
composition axis is scaled in weight percent, the phase fractions computed using the lever
rule are mass fractions—the mass (or weight) of a specific phase divided by the total alloy
mass (or weight). The mass of each phase is computed from the product of each phase
fraction and the total alloy mass.

DEVELOPMENT OF MICROSTRUCTURE IN ISOMORPHOUS ALLOY

 Consider an alloy of composition 36% Ni-64% Cu as it is cooled from 1300degree C.
Cooling follows vertical dashed line. Refer Fig. At point A alloy is in liquid state (L)
with36% Ni. When point B (1265 degree C) is reached solidification begins. The first
solid crystals of α get formed. Microstructure shows tiny crystals of α containing 47%
Ni in a liquid of 36% Ni. When melt is further cooled, more crystals are formed and
existing crystals grow. Composition of liquid and solid changes following liquidus and
solidus curves. At point C, liquid contains 32% Ni while solid contains 43% Ni. Above B
there is 100% liquid and below D it is 100% solid. α increases from 0% to 100% while
the temperature falls from point B to Point D . At point E there is only α solid solution
phase with a composition of 36% Ni

2) BINARY EUTECTIC SYSTEMS

• A eutectic system is a homogeneous mixture of substances that melts or solidifies
at a lower temperature than any of its individual components. This temperature is
known as the eutectic temperature.
• An example of a simple eutectic system is shown in Figure. Here the components
are completely soluble in liquid state and completely insoluble in solid state. The
eutectic reaction is:L → S1 +S2 on cooling. It means that 2 separate solid phases
are formed from a liquid of definite composition. It is an invariant reaction,
meaning zero degree of freedom (F= C-P+1= 2-3+1=0). There is a definite
composition (eutectic composition) and temperature (eutectic temperature). The
point where eutectic temperature and eutectic composition meet is known as
eutectic point. Eutectic means easy to melt.
• Eutectic alloy has the lowest melting point. It solidifies like a pure metal at
constant temperature

EUTECTIC SYSTEM WITH LIMITED SOLID SOLUBILITY

 A binary eutectic phase diagram (e.g., copper–silver system) shows how mixtures of two
metals solidify and transform at various compositions and temperatures. Key features of
such diagrams include:
Phases and Structures
• Three single-phase regions: liquid, α (Cu-rich solid solution), and β (Ag-rich solid
solution), both having FCC structures.
• Three two-phase regions: α + L, β + L, and α + β. Eutectic Point and Reaction Occurs at
a fixed composition (CE) and temperature (TE): For Cu–Ag: CE = 71.9 wt% Ag, TE
779°C. Eutectic reaction (on cooling): L(71.9 wt% Ag) ⇌ α(8.0 wt% Ag) + β(91.2 wt%
Ag)This is an invariant reaction, happening at constant T and specific compositions.
Lines and Regions
• Liquidus lines: AE and FE — mark where melting starts. Solidus lines: AB, GF, and the
eutectic isotherm (BEG) — lowest temperature for liquid phase to exist.
• Solvus lines: Separate single solid phases from solid + solid regions (e.g., α from α + β).
Important Behaviors
• Upon adding Ag to Cu or Cu to Ag, the melting point lowers.
• Isothermal solidification occurs at TE during the eutectic reaction, forming two solid
phases. Only two phases can coexist in equilibrium, except at the eutectic isotherm
where all three (α, β, L) can coexist.

Example: Lead–Tin (Pb–Sn) System

• Similar eutectic behavior.

• Eutectic point: 61.9 wt% Sn, 183°C.
• Used in 60–40 solder (60 wt% Sn, 40 wt% Pb), which melts completely at ~185°C —
ideal for low-temp soldering.

DEVELOPMENT OF MICROSTRUCTURE IN EUTECTIC ALLOYS

The microstructure of binary eutectic alloys depends on composition and the cooling path.
The lead–tin (Pb–Sn) system demonstrates several distinct cases:

Case 1: Compositions Below Solubility Limits at Room Temperature

• Example: C1 (e.g., 1 wt% Sn)
• On cooling: Alloy solidifies into a single-phase solid solution (α or β).
• Microstructure: Uniform polycrystalline structure of one phase (either α or β), no
changes occur upon further cooling.

Case 2: Compositions Between Solubility at Room Temp and at Eutectic

Temperature
• Example: C2 (e.g., 10 wt% Sn)
• Initial solidification yields α (or β) grains.As the temperature drops below the solvus
line, excess solute precipitates out as fine particles of the second phase.
 • Microstructure: Primary solid grains (e.g., α) + precipitated second phase (e.g., β).

Case 3: Eutectic Composition (61.9 wt% Sn)

• Example: C3 (61.9 wt% Sn)
• At 183°C, liquid transforms into eutectic mixture:
L ⇌ α (18.3 wt% Sn) + β (97.8 wt% Sn)
• Microstructure: Alternating lamellae of α and β called the eutectic structure.This
transformation occurs isothermally and by diffusion, forming layers for efficient atomic
exchange.

Case 4: Compositions Near but Not at Eutectic

• Example: C4 (~40 wt% Sn)
• Solidification begins with formation of primary α (or β). Remaining liquid (now
eutectic composition) solidifies at 183°C into eutectic structure.
• Microstructure: Contains primary phase + eutectic microconstituent .Primary phase:
Forms first from the liquid (e.g., α).Eutectic microconstituent: Lamellar mixture of α +
β formed later from eutectic liquid.

3) EUTECTOID AND PERITECTIC REACTIONS

Eutectoid Reaction
• Definition: A solid phase transforms into two new solid phases upon cooling at a single
temperature and fixed composition.
• Occurs at 560°C and 74 wt% Zn–26 wt% Cu. Reaction :γ → α + β (on cooling)
(Reverse occurs on heating)
• Compositions of product phases: α: 70 wt% Zn–30 wt% Cu . β: 78 wt% Zn–22 wt% Cu
• Type: Eutectoid (solid → solid + solid). Point E in phase diagram marks this eutectoid
reaction.
 • Importance: Eutectoid reactions (like in Fe–C system) are critical in heat treatment of
steels

Peritectic Reaction
• Definition: A solid and liquid phase combine to form a new solid phase upon cooling
(or reverse upon heating).
• Example in Cu–Zn system: Occurs at 598°C and 78.6 wt% Zn–21.4 wt% Cu. Reaction:
β + L → γ (on cooling)
• Point P on phase diagram represents this peritectic. Other perieutectics in Cu–Zn
occur around: 97 wt% Zn, 435°C:
η → ε + L . Additional peritectics involve transformations between ε, γ, δ intermediate
solid solutions.

Coring
In an isomorphous (solid solution) system, the first solid is richer in high melting
constituent. The concentration of the element having high melting point decreases (the
component with lower melting point increases) progressively from centre of the grain to
grain boundary. This variation in composition from the centre of each grain to its grain
boundary is called coring (a type of segregation). Coring can be removed by
homogenization (keeping at elevated temperature for sufficient time)

THE IRON–IRON CARBIDE (Fe–Fe3C) PHASE

DIAGRAM
The most important binary alloy system is Fe-C system. Primary engineering materials namely
steels and cast irons are alloys belonging to this system. Steel is the most widelyused material
in the world.
Iron-Carbon Equilibrium Diagram
Fe-C equilibrium (phase) diagram can be divided into 2 parts. (a) iron rich portion containing
up to 6.67 weight %C and (b) other portion containing 6.67-100% C (known as graphite. At
6.67% C, the entire structure is cementite (an intermetallic compound Fe3C). Hence the iron
rich portion of iron-carbon diagram can be called Fe- Fe3C phase diagram. The other portion
containing 6.67-100% C does not have any technical or commercial importance. Hence Fe-
Fe3C diagram is the iron-carbon diagram of practical importance. Refer Figure In Fe-C diagram
there are 5 different phases and 3 invariant reactions under equilibrium cooling condition
(very slow rate of cooling).

• The family of Fe-C alloys with carbon content up to 2.14% is called steels. When
carbon content is more than 2.14% up to 6.67 %, the alloys are called cast irons.

Phases in Fe-C diagram

1. ∂ Ferrite: ∂ ferrite is a stable phase only in the temperature range of 1394- 1538 degree C.
Maximum solubility of C in ∂ferrite is only 0.09% at 1495 degree C. This phase is not of much
significance.
2. α Ferrite: It is an interstitial solid solution of C in BCC iron. Maximum solubility is 0.022% C
at 727 degree C. At room temperature the solubility is only 0.008% C.
3. Austenite: It is an interstitial solid solution of C in FCC iron. Solubility of C in austenite is
much higher (≈100 times) than in BCC iron. Maximum solubility is 2.14 % at 1147 degree C.
Austenite is known as γ phase. It is stable in the temperature range of 912-1394 degreeC.
Microstructure of austenite is given in Fig. The strength of austenite is higher than that of
pure iron. It is due to solid solution strengthening by C.
4. Cementite: Cementite is an intermetallic compound. It is iron carbide (Fe3C). It is formed
when carbon content is more than the solubility limit in iron. It is an extremely hard and
brittle phase. Properties of steel can be controlled by controlling the amount, size and shape
of cementite. It is a metastable phase. That is, cementite can remain indefinitely at room
temperature even though it is not a completely stable phase.
5. Liquid phase: It is the fifth phase in iron-carbon equilibrium diagram. Apart from these 5
phases, there are 2 phase mixtures in the Fe-C diagram.
(a) Pearlite: It is a mixture of 2 phases, ferrite and cementite. It is formed by the eutectoid
reaction at 727 degree C. It has the structure of alternate lamellae of ferrite and cementite.
(b) Ledeburite: It is formed by eutectic reaction. It is a mixture of austenite and cementite.

INVARIANT REACTIONS
1.PERITECTIC REACTION

2. EUTECTIC REACTION:
It occurs at 1147 degree C. Liquid of 4.3% C solidifies into a mixture of two solid phases,
austenite (2.14% C) and cementite (6.67% C). This eutectic mixture is called ledeburite. Liquid
↔ austenite + cementite (on cooling→/heating ←)
3. EUTECTOID REACTION:
It is the most important reaction in Fe-C diagram. This reaction can be controlled by slowing
it, speeding it or completely avoiding it to obtain desired properties. Eutectoid reaction occurs
at 727degree C. Austenite of 0.77%C decomposes into a mixture of ferrite( 0.22% C) and
cementite (6.67% C). Austenite (solid 1) ↔ α ferrite (solid 2) + cementite (solid 3). The
eutectoid mixture of ferrite and cementite as alternate lamellae is known as pearlite.

DEVELOPMENT OF MICROSTRUCTURE OF FE-C

ALLOYS
1) EUTECTOID STEELS

Consider cooling of an alloy containing 0.77%C from 900 degree C (along PQ).At point P the
structure is fully austenite. At Q austenite transforms to a mixture of 2 phases, α ferrite and
cementite at 727 degree C. Slow cooling results in a microstructure consisting of alternate
layers or lamellae of ferrite (thick light layer) and cementite (thin dark layer). This structure
is known as pearlite. The name comes from the colour of mother of pearl seen in the
specimen. Mechanical properties are between soft ductile ferrite and hard brittle
cementite.

2)Hypoeutectoid Alloys

Hypoeutectoid means “less than eutectoid” (< 0.77% C). Consider an alloy of 0.4% C (RSTU
line)

• .At R (850 degree C): fully austenite (γ) grains.

• At S: A3 line is crossed. α ferrite nucleates on γ boundaries.
• At T (730 degree C): C content of austenite approaches 0.77% and C content of
ferrite reaches 0.22%.
• At U : The eutectoid temperature is crossed. Austenite transforms to pearlite.
Microstructure includes proeutectoid ferrite surrounded by pearlite. Large white
regions are proeutectoid ferrite. Dark patches with alternate lamellae are pearlite
3)Hypereutectoid Alloys

Consider cooling of a steel containing 1.4 % C at 900 degree C.

• At point V: austenite grains of 1.4% C

• At W: Cementite nucleates along austenite grain boundaries. Cementite contains
6.67%C. Hence austenite becomes poorer in C ( near to 0.77%C).
• At X: Eutectoid temperature is crossed. Austenite transforms to pearlite with
alternate lamellae of ferrite and cementite.
• At Y: Microstructure consist of proeutectoid cementite and eutectic pearlite.
Proeutectoid cementite appears lighter than eutectoid cementite in pearlite.
4) CAST IRON

➢ Fe-C alloys containing 2.14-6.67 %C are called cast irons. But useful alloys contain
C only up to 4.5%. Alloy containing 4.3%C is called eutectic cast iron. Alloys with
<4.3 %C are hypoeutectic cast irons and those with > 4.3 %C are hyper eutectic
cast irons. Consider cooling of a cast iron of 3% C from 1300 degree C.
• At point A: alloy is in liquid state.
• At B: liquidus line is crossed. Austenite starts to separate out from liquid.
Austenite has less carbon. Hence liquid becomes richer in C.
• At C: Eutectic temperature of 1147 degree C crossed. Liquid of 4.3% C converts to
ledeburite ( a mixture of austenite and cementite). Microstructure contains
proeutectic austenite and ledeburite.
 • At D: As temperature is lowered below eutectic temperature, more cementite
forms. Hence C in austenite reduces. At eutectoid temperature, austenite
contains 0.77%C. The austenite converts to pearlite. At D the microstructure
contains proeutectoid cementite and pearlite.
➢ In cast irons cementite is much more than in steels. Hence cast irons are more
brittle . Another type of microstructure is possible in cast irons under following
conditions: (a) high carbon content near to 4.3%C. (b) high cooling rates and (c )
silicon added as inoculant. The structure in these cases consists of graphite flakes
in a matrix of ferrite. Such cast irons are called grey cast iron. Cast irons with
cementite are known as white cast iron.

TRANSFORMATION OF AUSTENITE
1. Pearlite
• Pearlite is formed by diffusion of carbon. Carbon in austenite is re-distributed into 2
phases (a) carbon rich cementite and (b) low carbon ferrite. When cooling rate is
slow, coarse pearlite is formed. It consists of thick lamellae (layers) of ferrite and
cementite.
• At higher cooling rates, fine pearlite is obtained with fine layers of ferrite and
cementite. Cementite is hard and brittle. Ferrite is soft and ductile. In fine pearlite,
layers are more. Fine pearlite is harder and stronger with somewhat lower ductility.
Coarse pearlite has more ductility at the cost of hardness and strength.

2. Bainite
• Bainite is also a mixture of 2 phases, ferrite and cementite. But the distribution is
finer than in pearlite. Bainite forms as needles or plates. Transformation temperature
below nose of TTT diagram can only produce bainite. Hence bainite is usually formed
as an isothermal transformation. Bainite formed at just below nose of TTT is called
coarse (or upper) pearlite. At lower temperatures, lower or acicular bainite is
produced. Bainite has more strength and hardness than pearlite.

3.Martensite
• Martensite transformation occurs when cooling rate is very high. There is no
diffusion. It is formed in a very sudden and a thermal fashion. Reorientation of iron
and carbon atom into a body centered tetragonal (BCT) structure occurs.

4.Spheroidite
• Spheroidite structure is obtained by spheroidizing heat treatment. This structure has
improved machinability and ductility especially in hyper eutectoid steel. A structure
of spheroids of cementite in ferrite matrix is obtained. This is the softest state of
hyper eutectoid steels.
 HEAT TREATMENT
• Heat treatment is defined as a combination of heating and cooling applied on a metal
or alloy in solid state to produce desired properties. Main objectives of het treatment
are: (i) improve strength, ductility, impact strength etc. (ii) improve surface hardness
(iii) improve resistance to wear, heat and corrosion (iv) improve machinability
(v)refine grain size (vi) relieve internal stresses etc.

TTT Diagram for Eutectoid Steel

Phase diagrams have following limitations
1. They give no information on form and distribution of phases (lamellae,spheroids etc)
2. They give data corresponding to equilibrium condition (very slow rate of cooling/heating).
Such conditions are rarely achieved. Deviations from equilibrium condition can result in new
phases (quenching produces bainite, martensite etc

Temperature and cooling rate (time) affect transformation of austenite critically. Let us take a
eutectoid steel.
 • Transformation of austenite to pearlite at 650 degree C is given in Fig (a). Such curves
are prepared for various temperatures below eutectoid temperature. The data is
plotted as an isothermal transformation (time temperature transformation or TTT)
diagram.X axis gives time in log scale. Y axis gives temperature.
• Solid curve on left (Ps) indicates time of starting the transformation to pearlite. Curve
on right (Pf) gives time to complete pearlite conversion.
• Dashed curve provides time to complete 50% conversion at each temperature.
Towards left side of Ps only unstable austenite is present. Only pearlite exists to the
right of Pf . Just below eutectoid temperature, coarse pearlite( thick layers of ferrite
and cementite) is seen.
• At lower temperatures (apprx. 540 degree C), fine pearlite (thin layers of ferrite and
cementite) is observed.
• Isothermal holding below 540 degree C produces a new microstructure called
bainite. It also contains ferrite and cementite. But cementite is present as feathers or
needles. TTT diagram after extending up to 215 degree C is given in fig. All 3 curves
are C shaped. There is a nose near 540 degree C where transformation is fastest.
• Bainite formed just below nose is called upper bainite. In this bainite, cementite is
feathery. At lower temperatures, cementite becomes finer. It takes acicular or needle
like shape. This is called lower bainite.
• Rapid cooling (quenching) converts austenite into another structure called
martensite. It is a diffusionless and very fast transformation. It does not depend on
time. But it is a function of temperature to which alloy is quenched.Martensite does
not appear in Fe-C diagram because it is a non-equlibrium phase. But TTT diagram
shows martensite transformation. Ms indicates beginning of martensite
transformation. M50 and M90 indicate 50% and 90% transformation.
Use of TTT Diagrams
Practically all transformations take place under non-equilibrium conditions. Hence Fe-C
phase diagram cannot predict microstructure and properties. TTT diagram indicate
phases stable at various temperatures and times (cooling rates). Therefore, they can
predict and select the cooling rates to obtain desired microstructure and properties.

CCT DIAGRAM
CCT diagrams represent the transformation behavior of steel when cooled continuously,
rather than held at constant temperature like in TTT diagrams. They are more practical and
relevant for industrial heat treatments of steel.
• Continuous Cooling vs. Isothermal:
o Isothermal treatments require rapid cooling to a specific temperature and
holding it — often impractical.
o In reality, cooling is continuous, so the CCT diagram modifies TTT curves by
shifting them to longer times and lower temperatures.
 • Microstructure Formation:
o Fast cooling → Fine pearlite
o Slow cooling → Coarse pearlite
o Very rapid cooling (above critical rate) → Martensite
o Intermediate cooling rates → Mixtures of martensite and pearlite
• Bainite Formation:
o In plain carbon steels, bainite rarely forms during continuous cooling because
the transformation to pearlite completes before bainite can start.
• Martensite on CCT Diagrams:
o The transformation begins at M(start) and proceeds at M(50%) and M(90%)
temperatures.These lines are the same in both TTT and CCT diagrams.
Martensitic transformation is a thermal and time-independent.
• Critical Cooling Rate:
The minimum rate needed to avoid any pearlite or bainite and produce 100% martensite.
Alloying elements like Cr, Ni, Mo, Mn, W, and C delay pearlite and bainite formation, thereby
lowering the critical cooling rate and allowing martensite to form even in thicker sections.
• Effect of Composition:
Steels with < 0.25 wt% C are difficult to harden because they require unrealistically
fast quenching. Alloying elements must be in solid solution with austenite before
quenching to affect hardenability.

ANNEALING
1. Process Annealing
It is used to increase ductility of cold worked material to facilitate further deformation.
Machinability is also improved. It is used for low carbon steels. Steel is heated to 550-650
degree C, held for sufficient time and slowly cooled in air.

2.Full Annealing
This process is used to obtain complete recrystallization, relieve internal stresses and to
restore ductility &machinability.

• Hypoeutectoid steels are heated 50-90 degree C above A3 line. Holding at this
temperature converts the structure into austenite. Then the steels are very slowly
cooled (10-20 degree C) in the furnace. Austenite transforms to ferrite and pearlite.
Along with this, recrystallization, relief of internal stresses and restoration of
ductility are also achieved.
• Hyper eutectoid steels with pearlite + cementite structure are heated 50-90 degree
C above A1 line only. They are held at the temperature to convert pearlite into
austentite. There is no change to cementite.
• Then the steels are cooled slowly in the furnace. Austenite transforms to coarse
pearlite. Other required objectives of annealing are also met. These steels are not
heated to full austenite range (above Acm line) because machinability is drastically
affected due to brittle cementite film around pearlite.

SPHEROIDIZING
 • It is used to improve machinability and ductility of hyper eutectoid steel. Ref Fig.Steel
is heated to about 30 degree C below A1 line. It is held at this temperature for
sufficient time and then cooled very slowly in the furnace. A structure of spheroids of
cementite in ferrite matrix is obtained. This is the softest state of hypereutectoid
steels.

NORMALIZING
• Normalizing uses a higher cooling rate (cooling in air) compared to annealing (cooling
in furnace). A fine pearlite structure is obtained. It is used to obtain a good
combination of strength and ductility. Strength is much higher than annealing. It is
commonly used as a finishing operation after manufacturing.
• Ref fig.Steels are heated to about 50 degree C above A3 line for hypo eutectoid
steels and Acm line for hyper eutectoid steels. They are held at this temperature for
sufficient time and the entire structure changes to austenite. They are then cooled in
air. Pearlite in the structure forms as fine lamellae. Normalizing prevents brittle film
formation of cementite as a result of fast cooling rate.
 HARDENING
• Hardening is done to increase hardness, strength and wear resistance of steel by
obtaining a suitable microstructure after tempering.
• First step is austenitizing. Temperature range is the same as that used for annealing
(above A3 line for hypo and above A1 line for hyper eutectoid steels). Hyper
eutectoid steels are heated to above A1 line only because proeutectoid cementite is
itself a very hard phase. Steel is held at this temperature for sufficient time. It is then
quenched in water, oil or brine.
• The cooling rate should be above critical cooling rate to obtain full martensite.
Martensite has body centred tetragonal (BCT) structure. BCT has no close packed
plane. Hence dislocations cannot move easily and results in high hardness.
Martensite can absorb any amount of C in steel up to 0.77%.Highest hardness is
obtained for eutectoid steel (0.77%C).
• Cementite is hard, but has lower hardness than 0.77%C martensite. Hence hyper
eutectoid steels with martensite +cementite structure are not as hard as eutectoid
steel after hardening.
• Plain carbon steel when quenched in brine gave 60 HRc. The same steel by oil
quenching gave only 28HRc. Water and oil are the most widely used quenching
media. Quenching effect can be increased by agitation and circulation of the bath.

TEMPERING
• After hardening, the steels are brittle, though they have high hardness and strength.
Tempering reduces brittleness by relieving internal stresses and changing the
microstructure. Tempering involves reheating hardened steel to temperature below
A1 line, followed by slow cooling.
• Heat treatment cycle for hardening and tempering is shown in Fig. Tempering may be
done at low (150- 250 Degree C), medium(300-450 degree C) or high(450-680 degree
C) temperature .Low temperature tempering relieves internal stresses. Medium
temperature tempering produces a microstructure of martensite + troostite (very
fine pearlite). This increases ductility. High temperature tempering transforms
martensite to sorbite. This structure results in optimum combination of strength and
ductility.

SURFACE HARDENING TECHNIQUES

The various surface hardening treatments can be classified into two types:
1. No change in surface composition Methods :-(i) Flame hardening (ii) Induction hardening
(iii)Laser hardening
2. Change in surface composition methods:- (i) Carburizing (ii) Nitriding

1. FLAME HARDENING
In flame hardening an ordinary oxy acetylene torch is used to heat the part at the regions to
be hardened. Flame is slightly oxidizing in nature. The flame is adjusted to achieve a
temperature of about850 degree C. The torch is moved to heat the part uniformly. It is then
quenched by the jet of water from nozzle. Carbon content should be between 0.3-0.6
percent. Tempering is done after flame hardening.

Advantages
• Rapid and efficient method. Deep cases up to 6mm.
• Small regions (zones) can be hardened. Hence low distortions.
• Also suitable for large components that cannot be fitted in furnace and for heavy
components which cannot be transported.

Disadvantages
• Case depth is difficult to control. Hence thin cases are difficult.
• Low carbon steel cannot be hardened.

Applications
• Gear teeth, cylindrical pins, lathe beds, cam surface, engine push rods, pulleys and
sprocket teeth.

2.INDUCTION HARDENING
Induction hardening can produce a hard and wear resistant surface with a soft core. Job to be
hardened is placed within an induction coil of several turns of copper wire. A high frequency
current is passed. This sets up an induced alternating current which heats the job surface to a
temperature of 750-800 degree C. Heated surface is quickly quenched by water.

Advantages
 • Very fast process. Hardening to a depth of 0.8 mm can be achieved within 1 to 5
seconds.
• Irregular shapes can be hardened easily. Current dips into crevices and holes.
• Case depth can be controlled effectively by varying frequency, current and time.
• Outstanding resistance to warpage, distortion, oxidation and scaling. This is due to
small heating time and small portion being heated at a time.
• Unskilled operators can be employed
• Environment is clean.

Disadvantages
• Medium carbon steel containing 0.35 to0.60% can be hardened. Low carbon and low
nitrogen steels cannot be used.
• Hardness depends on carbon content. If carbon content is low, high hardness is
possible only in expensive high alloy steels.

Applications
Cams, gear teeth, shaft splines, bearing surfaces, pump shafts, piston rods, chain links etc.

3.LASER HARDENING
It is a variant of flame hardening. A phosphate coating is applied over the steel surface to
facilitate laser absorption. Selected areas are exposed to laser energy. The surface gets
heated to 900-1400 degree C. Heat can be controlled by varying power of laser. Parts are then
self -quenched (transferring heat to cooler surface) and tempered. Case depth is usually 0.1 to
1.5 mm.

Advantages
• Process is precise. Selective areas can be hardened accurately.
• Useful for ferrous materials containing more than 0.2% carbon. Steels and cast irons
can be hardened.
• Minimum distortion.
• Core remains soft.
• Process is environmentally clean. Work piece need not be cleaned.

Applications
Process is primarily used in automobile industry for axle shaft housings, power steering gear
housings etc..
4.CARBURIZING
It involves adding excess carbon to surface of steel. Surface carbon may be about 1.2% while
interior may be mild steel (less than 0.25% C). The process involves heating the parts with a
carbon rich substance above critical temperature for a long time. There are 3 carburizing
methods.
(a).Solid carburizing (pack carburizing):- Solid substances such as coke, coal, charcoal, calcium
carbonate etc are used. The steel parts are placed in a closed chamber filled with carbon rich
solid powder. Chamber is heated to 870-980 degree C and held at the temperature for 5-10
hours. At this temp steel is austenitized. Carbon enters the surface up to a level of 1.2%. It is a
slow, dirty, effective and cheap process.
(b).Gas Carburizing:- Parts are heated in a furnace filled with carbon rich gases such as
methane, propane, butane etc. Temperature is 820-980 degree C and sufficient holding time
is given. Hydrocarbons decompose and carbon gets deposited on the surface. This process is
faster than pack carburizing. Case depth can be controlled more accurately. But it is more
expensive.
(c)Liquid carburizing:- In this process liquid hydrocarbons are used. Immersing in the liquid
bath or spraying methods are employed. Components are heated to 820-980 degree C. Bath
is prepared with NaCN, Na2CO3 and NaCl. The process is faster and more efficient.

5.NITRIDING
Nitriding is very effective for alloy steels containing strong nitride forming elements like Al, Cr,
Mo, V and W. Process involves heating to 650 degree C and holding at 650 degree C in an
atmosphere of NH3 gas for 20-100 hrs. NH3 decomposes into N & H. N penetrates into the
surface of steel and forms hard nitrides. Parts are cooled in furnace. Nitriding improves
corrosion resistance, but the process is costly and time consuming.

BASICS OF FATIGUE AND CREEP

FATIGUE
• ASTM definition of fatigue: Fatigue is the process of progressive, localized, permanent
structural changes occurring in a material subjected to fluctuating stresses and strains
at some point or points which may culminate in cracks or complete fracture after
sufficient number of fluctuations.
• Materials subjected to alternating (also called repetitive, cyclic or fluctuating stresses)
will fail at a much lower stress compared to those loaded with steady stresses.
Behavior of materials under such fluctuating or cyclic stresses is called fatigue.
• Rotating shafts, bridges, machine components, automobile parts etc. are some of the
components subjected to fatigue. Fatigue is observed in all types of materials. More
 than 80% failure in metallic materials is due to fatigue. It is very dangerous because
failure occurs without any warning in a brittle fashion.

S-N Curve
• Fatigue is represented by a curve called S-N curve. Typical S-N curves for alloy steel
and aluminium alloys are shown in figure.
• Fatigue test is conducted on a specimen by stress cycling at a maximum stress
amplitude of σ max (less than tensile strength). No of cycles to failure is counted. Test
is repeated at progressively lower stress levels. A plot of stress (S) versus log number
of cycles to failure (log N) is prepared. This is the S-N curve for the material.
• In general, higher the stress lower is the cycles to failure. For materials like steel, S-N
curve become horizontal at higher N values. Corresponding stress level at horizontal
portion is called Endurance Limit. It is the largest fluctuating stress which will not
cause failure after infinite number of cycles. Generally it is 40-50% of tensile strength.
For materials like aluminium alloys there is no specific endurance limit. In such
materials, fatigue strength is taken as the stress level at which failure occurs after a
given number of cycles (usually 107 cycles).

FACTORS AFFECTING FATIGUE STRENGTH

1.Stress Concentration
• Non-uniformities like steps at change in cross section, collars, holes, abrupt corners,
key ways, grooves, threads, spline, press fitted/shrink fitted attachments etc. are
primary stress concentrations.
• Surface discontinuities arising from fabrication such as surface roughness, seams,
nicks, notches, machining marks, identification marks, forging laps, pitting and
corrosion and internal discontinuities like porosity, inclusions, cracks and voids come
under the category of secondary stress concentration. All these can reduce fatigue
strength drastically.
• Stress concentration factor is the ratio of stress in a notched specimen to the stress in
an unnotched specimen of same material.

2.Size Effect
 • Generally, larger component has more number of imperfections (defects) and hence
lower fatigue strength. In carbon steel, it has been found that fatigue factor is 1 for
diameter less than 10mm, 0.9 for diameter between 10 and 50 mm and 1− (D−0.76
/380) for diameter between 50 and 230 mm.

3.Surface Roughness
• Generally maximum stress occurs at the surface. The surface is also exposed to harsh
environments like corrosion and unexpected loads like impact. Therefore surface
roughness has a significant effect on fatigue strength. Rough surface gives much lower
fatigue life than fine surface

4.Change in Surface Properties

• Decarburization at the surface of steel significantly reduces fatigue strength. The
strength can be regained by recarburizing the surface. Surface alloying methods like
carburizing, nitriding and carbonitriding can appreciably increase fatigue strength.
Surface hardening processes using flame, induction, laser and electron beam also
improves fatigue strength. Mechanical working of the surface of steel part by shot
peening and skin rolling enhances the fatigue strength.

5.Surface Residual Stress

• Residual stresses are produced by fabrication and finishing operations. Residual
stresses on the surface can seriously affect fatigue properties. Compressive residual
stresses at the surface of a part increase fatigue appreciably. Tensile residual stresses
at the surface reduce the fatigue strength. Compressive residual stresses may be
produced by surface alloying, surface hardening and mechanical working of the
surface.

CREEP
• Creep is defined as the time dependent strain when load is applied continuously over
a long period of time. Creep can become very large and result in final fracture without
any increase in load. Some components in which creep occurs are turbine rotors in
steam engines and jet engines, beams in roof of buildings, high pressure pipe lines
etc. Creep occurs in all materials at all temperatures.
• However it is more pronounced at high temperature, generally above 0.4 Tm (Tm =
melting temperature in K) for metallic materials. Amorphous polymers like plastics
exhibit creep even at room temperature. Creep stress is generally much below the
yield stress.

FACTORS AFFECTING CREEP

1.Temperature
 • Creep becomes significant at high temperatures (usually > 0.4 Tm). As temperature
increases, the rate of creep increases due to enhanced atomic diffusion and
dislocation motion.

2. Applied Stress
• Higher applied stress increases the creep rate. At elevated stresses, dislocation motion
and diffusion processes become more active.

3. Time
• Since creep is a time-dependent process, the duration of applied stress matters.
Longer exposure increases total deformation.

4. Material Structure
• Grain size: Fine grains improve strength at lower temperatures but accelerate creep at
high temperatures due to grain boundary sliding. Coarser grains resist creep better.
• Crystal structure: Materials with face-centered cubic (FCC) structures generally exhibit
more creep than body-centered cubic (BCC) ones because of their more closely
packed planes allowing easier atomic movement.
• Alloying: Strengthening mechanisms like solid solution strengthening, precipitation
hardening, and dispersion strengthening can reduce creep.

5. Environment
• Exposure to oxidizing or corrosive environments can degrade material properties and
accelerate creep.

6. Loading Type
• Constant stress versus cyclic loading can affect creep performance.
• Multiaxial stress states may also impact creep more severely than uniaxial stress.