MMEN 120

Solidification and Phase Diagrams

 Solidification
 When molten alloys are cast, solidification starts at the
walls of the mold as it is being cooled.
 The solidification of an alloy (as opposed to a pure metal)
takes place not at a specific temperature but over a range
of temperatures.
 While the alloy is in this range, it has a pasty form that
consists of solid, treelike structures called dendrites
(meaning treelike), and liquid metal.
 The size and shape of the dendrite depends on the cooling
rate.
 The liquid metal existing among these three-dimensional
dendritic structures eventually solidifies to form a
completely solid structure that we refer to as the grain
structure.
 The study of dendrites is important because they influence
compositional variations, porosity, and segregation and Fig. A “forest” of dendrites formed during
therefore the properties of the cast metal. the solidification of a nickel-based
superalloy
 Solidification
 The solidification of metals and alloys is an important industrial process since most metals are melted
and then cast into a semifinished or finished shape.
 The solidification of a metal or alloy can be divided into the following steps:
 The formation of stable nuclei in the melt (nucleation)
 Homogeneous nucleation
 Heterogeneous nucleation
 The growth of nuclei into crystals and the formation of a grain structure

Fig. Schematic illustration showing

the several stages in the
solidification of metals:
(a) formation of nuclei,
(b) (b) growth of nuclei into crystals
(c) (c) joining together of crystals to
form grains and associated grain
boundaries.
Note that the grains are randomly
oriented.
 Solidification
Homogeneous Nucleation
 Homogeneous nucleation in a liquid melt occurs when the metal itself provides the atoms
needed to form nuclei.
 When a pure liquid metal is cooled below its equilibrium freezing temperature to a
sufficient degree, many homogeneous nuclei are created by slow-moving atoms bonding
together.
 Homogeneous nucleation usually requires a considerable amount of undercooling, which may be
as much as several hundred degrees Celsius for some metals.
 For a nucleus to be stable so that it can grow into a crystal, it must reach a critical size.
 A cluster of atoms bonded together that is less than the critical size is called an embryo,
and one that is larger than the critical size is called a nucleus.
 Because of their instability, embryos are continuously being formed and redissolved in the
molten metal due to the agitation of the atoms.
 Solidification
Heterogeneous nucleation
 Homogeneous nucleation in a liquid melt occurs when the metal itself provides the atoms
needed to form nuclei.
 nuclei form preferentially at structural inhomogeneities, such as container surfaces, insoluble
impurities, grain boundaries, dislocations e.t.c
 Heterogeneous nucleation refers to the is nucleation that occurs preferentially at structural
inhomogeneities, such as container surfaces, insoluble impurities, grain boundaries,
dislocations.
 For heterogeneous nucleation to take place, the solid nucleating agent (impurity solid or
container) must be wetted by the liquid metal.
 Heterogeneous nucleation takes place on the nucleating agent because the surface energy to
form a stable nucleus is lower on this material than in the pure liquid itself (homogeneous
nucleation).
 This process does not require large amounts of undercooling
 Solidification
Growth of Crystals in Liquid Metal
 After stable nuclei have been formed in a solidifying metal, these nuclei grow into crystal.
 In each solidifying crystal, the atoms are arranged in an essentially regular pattern, but the orientation
of each crystal varies.
 When solidification of the metal is finally completed, the crystals join together in different
orientations and form crystal boundaries.
 Solidified metal containing many crystals is said to be polycrystalline.
 The crystals in the solidified metal are called grains, and the surfaces between them are the grain
boundaries.
 The number of nucleation sites available to the freezing metal will affect the grain structure of the
solid metal produced.
 If relatively few nucleation sites are available during solidification, a coarse, or large-grain,
structure will be produced.
 If many nucleation sites are available during solidification, a fine-grain structure will result.
 A grain refiner is a material added to a molten metal to attain finer grains in the final grain structure.
 Examples of grain-refining elements include titanium, boron, or zirconium
 Solidification
Growth of Crystals in Liquid Metal
 When a relatively pure metal is cast into a stationary mold without the use of grain refiners, two major types
of grain structures are usually produced: (a) Equiaxed grains and (b) Columnar grains.

 Equiaxed grains:
 Formed when the nucleation and growth conditions in the
liquid metal during solidification are such that the crystals
can grow about equally in all directions.
 They are commonly found adjacent to a cold mold wall.
 Large amounts of undercooling near the wall create a
relatively high concentration of nuclei during solidification, a
condition necessary to produce the equiaxed grain structure.
 Columnar grains
 These are long, thin, coarse grains created when a metal
solidifies rather slowly in the presence of a steep
temperature gradient.
 Relatively few nuclei are available when columnar grains are
Fig. Schematic drawing of a solidified
produced.
metal grain structure produced by using a
cold mold.
 Solidification
Growth of Crystals in Liquid Metal

Fig. An image showing the equiaxed grains of a

Fig. Ingots of alloy 6063 (Al-0.7% Mg-0.4% Si). nickel– molybdenum alloy at a magnification of
(a) Columnar grains: Ingot section was cast without the addition of a grain 50,000.
refiner.
(b) Equiaxed grains: Ingot section was cast with the addition of a grain
refiner.
 Solidification
Single crystals
 Almost all engineering crystalline materials are composed of many crystals and are therefore polycrystalline.
 However, there are a few that consist of only one crystal and are therefore single crystals. Examples
include:
 High-temperature creep-resistant gas turbine blades.
 Single-crystal turbine blades are more creep resistant at high temperatures than the same blades
made with an equiaxed grain structure or a columnar grain structure
 The above is because at high temperatures above about half the absolute melting temperature of a
metal, the grain boundaries become weaker than the grain bodies, thus susceptible to creep.
 Silicon single crystals
 Are used in solid-state electronic integrated circuit chips.
 Single crystals are necessary for this application since grain boundaries would disrupt the flow of
electrons in devices made from semiconductor silicon.
 In growing single crystals, solidification must take place around a single nucleus so that no other crystals are
nucleated and grow.
 One of the commonly used techniques to produce high-quality (minimization of defects) silicon single
crystals is the Czochralski method.
 Solidification
Single crystals

Different grain structures of gas turbine airfoil blades:

(a) Polycrystal equiaxed
(b) (b) polycrystal columnar, and
(c) (c) single crystal.
 Metallic Solid Solutions
 Most engineering metals are combined with other metals or nonmetals to to impart specific characteristics
to the material.
 These include increased strength, higher corrosion resistance, or other desired properties.
 For example, in normal ambient environments, pure silver is highly corrosion resistant, but also very
soft. Alloying with copper significantly enhances the mechanical strength without depreciating the
corrosion resistance appreciably.
 A metal alloy, or simply an alloy, is a mixture of two or more metals or a metal (metals) and a nonmetal
(nonmetals).
 The simplest type of alloy is that of the solid solution.
 A solid solution is a solid that consists of two or more elements atomically dispersed in a single-phase
structure.
 With regard to solid solution;
 Solvent refers to the element or compound that is present in the greatest amount; on occasion, solvent
atoms are also called host atoms.
 Solute is used to denote an element or compound present in a minor concentration.
 A solid solution forms when, as the solute atoms are added to the solvent/host material, the crystal
structure is maintained and no new structures are formed.
 A solid solution is also compositionally homogeneous; the impurity atoms are randomly and uniformly
dispersed within the solid.
 Metallic Solid Solutions
How are solid solutions formed?
 Impurity point defects are found in solid solutions, of which there are two types: substitutional and interstitial.
Substitutional solid solution
 For the substitutional type, solute or impurity atoms replace or substitute for the host atoms
 The Hume–Rothery rules for extensive solid solution:
a. Atomic size factor: The diameters of the atoms of the elements must not
differ by more than about 15%.
b. Crystal structure: The crystal structures for metals of both atom types must
be the same.
c. Electronegativity factor:
 There should be no appreciable difference in the electronegativities of
the two elements
 Otherwise, the highly electropositive element will lose electrons, the
highly electronegative element will acquire electrons, and compound
formation will result.
d. Valences: Fig. Two-dimensional schematic
representations of substitutional and
 Solid solubility will be favored if the two elements have the same valence. interstitial impurity atoms.
 If there is a shortage of electrons between the atoms, the binding
between them will be upset, resulting in conditions unfavorable for solid
solubility.

 An example of solid solution is Cu-Ni.

 Metallic Solid Solutions
Interstitial solid solution
 In interstitial solutions, the solute atoms fit into the spaces
(interstices) between the solvent or parent atoms.
 The interstices available in a cubic crystal may be classified as:
 A cubic site if surrounded by eight neighbors (i.e., coordination
number is 8—does not occur in BCC or FCC crystals);
 Octahedral site if surrounded by six neighbors (i.e., the
coordination number is 6);
 In BCC, these sites are located at , 1, or other similar positions.

 In FCC, these sites are located at 0, , 1 and , , Fig: Schematic illustration of an interstitial
solid solution of carbon in FCC 𝛾 iron just
 Tetrahedral site if surrounded by four neighbors (i.e., the
above 912°C showing a (100) plane.
coordination number is 4).
Note the distortion of the iron atoms
 In BCC, these sites are located at 1, , or other similar positions. (0.129 nm radius) around the carbon atoms
(0.075 nm radius), fitting into voids of
 In FCC, these sites are located at , , or other similar positions.
0.053 nm radius.
 Examples of atoms that can form interstitial solid solutions due to
their small size are hydrogen, carbon, nitrogen, and oxygen.
 An important example of an interstitial solid solution is that formed
by carbon in FCC 𝛾 -gamma iron and BCC 𝛼 -alpha Iron.
 Phase Diagrams
What is the significance of phase diagrams?
The understanding of phase diagrams for alloy systems is extremely important because:
 The development of microstructure of an alloy is related to the characteristics of its phase
diagram.
 There is a strong correlation between microstructure and mechanical properties
 Phase diagrams provide valuable information about melting, casting, crystallization, and other
phenomena.
Components
 Components are pure metals and/or compounds of which an alloy is composed.
 For example, in a copper–zinc brass, the components are Cu and Zn.
System
 System relate to the series of possible alloys consisting of the same components but without
regard to alloy composition (e.g., the iron–carbon system).
 Solubility Limit
 Solubility limit refers to the maximum concentration of solute atoms that may dissolve in the solvent to form a solid
solution at some specific temperature for a given alloy system.
 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.

 Consider the sugar–water (C12H22O11–H2O) system. Sucrose/Water Phase Diagram

 Sugar is added to water, a sugar–water solution or syrup forms.
100
 As more sugar is introduced, the solution becomes more Solubility
concentrated, until the solubility limit is reached or the solution L

Temperature (°C)
80 Limit
becomes saturated with sugar.
 The solution is not capable of dissolving any more sugar, and
(liquid)
60 +
further additions simply settle to the bottom of the container. L
 Thus, the system now consists of two separate substances: a (liquid solution S
sugar–water syrup liquid solution and solid crystals of
40
i.e., syrup) (solid
undissolved sugar.
 The solubility limit of sugar in water depends on the 20 sugar)
temperature of the water
 Question: What is the solubility limit at 20°C? 0 20 40 6065 80 100
 Answer: 65 wt% sugar.

Sugar
Water
Co =Composition (wt% sugar)

Pure

Pure
o If Co < 65 wt% sugar: syrup
o If Co > 65 wt% sugar: syrup + sugar.
Fig: The solubility of sugar (C12H22O11–
H2O) in a sugar–water syrup.
 Phases
 A phase is 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.
 For example: the sugar–water syrup solution. Each has different physical properties (one is a liquid, the
other is a solid); furthermore, each is different chemically (i.e., has a different chemical composition);
one is virtually pure sugar, the other is a solution of H2O
 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 across which there will be a discontinuous and abrupt change in
physical and/or chemical characteristics
 When two phases are present in a system, it is not necessary that there be a difference in both physical and
chemical properties; a disparity in one or the other set of properties is sufficient. Example is water and ice
have dissimilar physical properties but same chemical makeup.
 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
 Microstructure
 Microstructure influence the physical properties and, in particular, the mechanical behavior of a material.
 In metal alloys, microstructure is characterized by the number of phases present, their proportions, and
the manner in which they are distributed or arranged.
 The microstructure of an alloy depends on such variables as the:
 Alloying elements present,
 Concentrations of alloying elements,
 Heat treatment of the alloy i.e.,
o The temperature
o The heating time at temperature
o The rate of cooling to room temperature).
b (lighter
phase)
 Microscopy is the observation of microstructure using some
type of microscope:
 Optical microscope (OM) a (darker
 Scanning electron microscope (SEM) and
 Transmission electron microscope (TEM). phase)

Aluminum- Copper Alloy

 Phase Equilibria
 A system is at equilibrium if its free energy is at a minimum under some specified combination of
temperature, pressure, and composition.

 In a macroscopic sense, the above means that the characteristics of the system do not change with time
but persist indefinitely; that is, the system is stable.

 A change in temperature, pressure, and/or composition for a system in equilibrium results in:
 An increase in the free energy and,

 A possible spontaneous change to another state by which the free energy is lowered.

 Phase equilibrium, refers to equilibrium as it applies to systems in which more than one phase may exist.

 Metastable: Refer to non-equilibrium state that may persist for a very long time (specially in solid systems,
that a state of equilibrium is never completely achieved because the rate of approach to equilibrium is
extremely slow)
 Phase diagram
 Phase diagram gives information about the control of microstructure or phase structure of a
particular alloy system and it is conveniently and concisely displayed (equilibrium or constitutional
diagram).

 There are three externally controllable parameters that will affect phase structure –

 Temperature,

 Pressure,

 Composition

 Phase diagram are constructed when combinations of the above parameters are plotted against one
another.
 One – component (or unary) phase diagram
 It is a one component system, in which composition is held constant ( i.e., the phase diagram is for a pure
substance); that is pressure and temperature are variable.
 This is one-component phase diagram (or unary phase diagram, sometimes also called a pressure–temperature
[or P–T] diagram)
 Example. Water H2O
 There exist three different phases—solid, liquid,
and vapor.
 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.
 All of the three phases are simultaneously in
equilibrium with one another at point O (triple point
or invariant point)
 Intersection of the dashed horizontal line at 1 atm
pressure with the solid– liquid phase boundary (point
2) corresponds to the melting point at this pressure
(T = 0 ℃).
 Similarly, point 3, the intersection with the
liquid–vapor boundary, represents the boiling point (T
= 100 ℃). Fig. Pressure–temperature phase diagram for H2O.
 Binary phase diagrams
 The most common type of phase diagrams are those in for which temperature and composition are
the variable parameters and pressure is held constant—normally 1 atm.

 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.

 Phase transformations refers to the changes in microstructure 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: Nickel – Copper system
 The composition ranges from 0 wt% Ni (100 wt% Cu) on the far
left horizontal extreme to 100 wt% Ni (0 wt% Cu) on the right.
 Three different phase regions, or fields, appear on the diagram: an
alpha (𝜶) field, a liquid (L) field, and a two-phase 𝜶 + 𝑳 field.
 The liquid L is a homogeneous liquid solution composed of both
copper and nickel.
 The alpha phase is a substitutional solid solution consisting of
both Cu and Ni atoms and has an FCC crystal structure.
 At temperatures below about 1080 ℃, copper and nickel are
mutually soluble in each other in the solid state for all
compositions. Reasons?
 Both Cu and Ni have the same crystal structure (FCC).
 Both Cu and Ni have nearly identical atomic radii
 Both Cu and Ni have identical electronegativities.
 Both Cu and Ni have similar valences
 The copper–nickel system is termed isomorphous because of this
complete liquid and solid solubility of the two components.
Fig. The copper–nickel phase diagram.
 Binary phase diagrams: Nickel – Copper system
 For metallic alloys, solid solutions are commonly designated by lowercase
Greek letters (𝜶, 𝜷 𝑎𝑛𝑑 𝜸, etc.).
 For phase boundaries:
 The line separating the L and a + L phase fields is termed the liquidus
line. The liquid phase is present at all temperatures and compositions
above this line.
 The solidus line is located between the 𝜶 𝒂𝒏𝒅 𝜶 + 𝑳 regions, below
which only the solid 𝛼 −phase exists.
 The solidus and liquidus lines intersect at the two composition
 Extremes corresp to the melting temperatures of the pure components.
 For example, the melting temperatures of pure copper and nickel are
1085oC and 1453oC, respectively.
 Heating pure copper corresponds to moving vertically up the left-hand
temperature axis.
 For pure components, melting and solidification occurs at a constant
temperature. Fig. The copper–nickel phase diagram.
 For any composition other than pure components, this melting phenomenon Upon heating of an alloy of composition 50 wt% Ni–
occurs over the range of temperatures between the solidus and liquidus 50 wt% Cu, melting begins at approx. 1280oC; the
lines; amount of liquid phase continuously increases with
 Both solid a and liquid phases are in equilibrium within this temperature temperature until about 1320oC , at which point the
alloy is completely liquid.
range.
 Interpretation of Phase Diagrams
 What type of information is available in a binary system of known
composition and temperature at equilibrium?

 the phases that are present.

 the compositions of these phases.

 the percentages or fractions of the phases.

 What information do you need to determine the phases present?

 Information on temperature and composition.

 For example

 An alloy of composition 60 wt% Ni–40 wt% Cu at 1100oC would be

located at point A.

 Because this is within the alpha region, only the single alpha
phase will be present.
Fig. The copper–nickel phase diagram.
 However, a 35 wt% Ni–65 wt% Cu alloy at 1250oC (point B)
consists of both alpha and liquid phases at equilibrium.
 Interpretation of Phase Diagrams
Determination of Phase Compositions
1. For a single phase region
 The composition of this phase is simply the same as the overall composition of the alloy.
 For example, consider the 60 wt% Ni–40 wt% Cu alloy at 1100oC (point A). At this composition and temperature, only
the alpha phase is present, having a composition of 60 wt% Ni–40 wt% Cu.
2. For a two phase region
 The following procedure is used.
a. A tie line is constructed across the two-phase region at the temperature of
the alloy.
b. The intersections of the tie line and the phase boundaries on either side are
noted.
c. Perpendiculars are dropped from these intersections to the horizontal
composition axis, from which the composition of each of the respective
phases is read.
 For example, consider the 35 wt% Ni–65 wt% Cu alloy at 1250℃, located at
point B and lying within the 𝜶 + 𝑳 phase region. What is the composition (in wt%
Ni and Cu) for both the 𝜶(𝒂𝒍𝒑𝒉𝒂) and liquid phases?
 The tie line is constructed across the 𝜶 + 𝑳 phase region, as shown.
 The perpendicular from the intersection of the tie line with the liquidus
boundary meets the composition axis at 31.5 wt% Ni–68.5 wt% Cu, which is the Fig. A portion of the copper–nickel
composition of the liquid phase, CL. phase diagram for which compositions
 Likewise, for the solidus–tie line intersection, we find a composition for the and phase amounts are determined at
𝜶(𝒂𝒍𝒑𝒉𝒂) solid solution phase, C𝜶, of 42.5 wt% Ni–57.5 wt% Cu. point B..
 Interpretation of Phase
Determination of Phase Amounts
Diagrams
1. For a single phase region
 Because only one phase is present, the alloy is composed entirely of that phase—that is, the phase fraction is 1.0, or,100%
 For the 60 wt% Ni–40 wt% Cu alloy at 1100℃ (point A ), only the 𝜶(𝒂𝒍𝒑𝒉𝒂) phase is present; hence, the alloy is completely, or
100%, 𝜶(𝒂𝒍𝒑𝒉𝒂) .
2. For a two phase region, lever rule (or the inverse lever rule) is used.
 The lever rule procedure.
a. The tie line is constructed across the two-phase region at the temperature of
the alloy.
b. The overall alloy composition is located on the tie line.
c. 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.
d. The fraction of the other phase is determined in the same manner.

𝑊 = = 𝑊 = =
f. If phase percentages are desired, each phase fraction is multiplied by 100.
 Note: When the composition axis is scaled in weight percent:
 The phase fractions computed using the lever rule are mass fractions.
 Mass fractions refer to 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.
 Interpretation of Phase Diagrams
Determination of Phase Amounts (example)
Consider again the example shown in Figure, for which at 1250℃ both 𝜶(𝒂𝒍𝒑𝒉𝒂) and
liquid phases are present for a 35 wt% Ni–65 wt% Cu alloy. Compute the fraction
of each of the 𝜶(𝒂𝒍𝒑𝒉𝒂) and liquid phases?
Solution
 Construct the tie line at the 1250℃.
 Let the overall alloy composition be located along the tie line and denoted as C0,
and let the mass fractions be represented by WL and Wa for the respective
phases.
 Note: In the use of the lever rule, tie line segment lengths may be determined
either by:
 Direct measurement from the phase diagram using a linear scale, preferably
graduated in millimeters, or
 By subtracting compositions as taken from the composition axis. Composition
need be specified in terms of only one of the constituents for a binary
alloy; for the preceding computation, weight percent nickel is used Fig. A portion of the copper–nickel
phase diagram for which compositions
.
𝑊 = = = = 0.68 and phase amounts are determined at
. .
point B..

.
𝑊 = = = = 0.32
. .
 Interpretation of Phase
Determination of Phase Amounts
Diagrams
 For multiphase alloys, at times it is more convenient to specify relative phase amount in terms of volume fraction
rather than mass fraction. Why?
 Phase volume fractions are preferred because:
 They (rather than mass fractions) may be determined from examination of the microstructure.
 The properties of a multiphase alloy may be estimated on the basis of volume fractions.
 Volume fraction of the 𝜶 phase (𝑉 ) , and Volume  Conversion of volume fractions of 𝜶 and 𝜷 phases to
fraction 𝜷 phase (𝑉 ) are defined as: mass fractions:
𝑉𝜌
𝑉 = 𝑉 = 𝑊 =
𝑉 𝜌 +𝑉 𝜌
where 𝒗𝜶 and 𝒗𝜷 denote the volumes of the respective phases in the alloy

 𝑉 +𝑉 =1
𝑉𝜌
 Conversion of mass fractions of 𝜶 and 𝜷 phases to 𝑊 =
volume fractions: 𝑉 𝜌 +𝑉 𝜌

𝑉 = 𝑉 =

where 𝝆𝜶 and 𝝆𝜷 denote the densities of the respective

phases in the alloy
 Development of Microstructure in Isomorphous Alloys
Equilibrium Cooling
 Let us consider the copper–nickel system, specifically an alloy of composition 35 wt% Ni–65 wt% Cu as it is cooled from 1300oC.

 Let us consider the Cu – Ni system, specifically an alloy of composition 35

wt% Ni–65 wt% Cu as it is cooled from 1300 ℃.
 Cooling of an alloy of this composition corresponds to moving down the
vertical dashed line.
 At 1300 ℃, point a, the alloy is completely liquid (of composition 35 wt%
Ni–65 wt% Cu) and has the microstructure represented by the circle insert
in the figure.
 As cooling begins, no microstructural or compositional changes will be
realized until we reach the liquidus line (point b, ~1260 ℃).
 At this point, the first solid 𝜶 (alpha) begins to form, which has a
composition dictated by the tie line drawn at this temperature [i.e.,
46 wt% Ni–54 wt% Cu, noted as 𝜶(46 Ni)]
 the composition of liquid is still approximately 35 wt% Ni–65 wt% Cu
[L(35 Ni)]
 With continued cooling, both compositions and relative amounts of each of
the phases will change.
 The compositions of the liquid and alpha phases will follow the liquidus
Fig. Schematic representation of the development of
and solidus lines, respectively. microstructure during the equilibrium solidification of a
35 wt% Ni–65 wt% Cu alloy.
 Development of Microstructure in Isomorphous Alloys
Equilibrium Cooling
 Note that the during cooling, the overall alloy composition (35 wt% Ni–65 wt% Cu) remains unchanged even though there is a
redistribution of copper and nickel between the phases.
 At 1250 ℃, point c , the compositions of the liquid and alpha phases are:
 Liquid phase - 32 wt% Ni–68 wt% Cu [L(32 Ni)]
 Alpha phase - 43 wt% Ni–57 wt% Cu [a(43 Ni)]
 The solidification process is virtually complete at about 1220℃, point d; the
composition of the solid alpha and last remaining liquid is:
 Alpha solid - approximately 35 wt% Ni–65 wt% Cu (the overall alloy
composition),
 Last remaining liquid is 24 wt% Ni–76 wt% Cu.
 Upon crossing the solidus line, this remaining liquid solidifies; the final product
then is a polycrystalline 𝜶-phase solid solution that has a uniform 35 wt% Ni–65
wt% Cu composition.
 Subsequent cooling produces no microstructural or compositional alterations.
 Note: Equilibrium solidification and the development of microstructures, as
described are realized only for extremely slow cooling rates. Why?
 With changes in temperature, there must be readjustments in the
compositions of the liquid and solid phases through diffusion.
 Because diffusion is a time-dependent phenomenon, to maintain equilibrium
during cooling, sufficient time must be allowed at each temperature for the Fig. Schematic representation of the development of
microstructure during the equilibrium solidification of a
appropriate compositional readjustments to occur. 35 wt% Ni–65 wt% Cu alloy.
 Binary Eutectic Phase Diagram
 This type of phase diagrams is found in alloys systems such as: Cu-Ag, Pb-Sn
The copper–silver Eutectic phase diagram.
 Three single-phase regions are found on the diagram: 𝜶, 𝜷 and 𝑳
 𝑨𝒍𝒑𝒉𝒂 𝜶 𝒑𝒉𝒂𝒔𝒆
 It is a solid solution Ag in Cu (rich in copper).
 It has silver as the solute component.
 The solubility limit of silver in the 𝜶 𝒑𝒉𝒂𝒔𝒆 corresponds
to the boundary line, labeled CBA.
 The boundary line CB is known as solvus while boundary
line BA is known as solidus.
 𝑩𝒆𝒕𝒂 𝜷 𝒑𝒉𝒂𝒔𝒆
 It is a solid solution of Cu in Ag ( rich in silver).
 It has copper as the solute component
 The solubility limit of copper in the 𝜷 𝒑𝒉𝒂𝒔𝒆 corresponds
to the boundary line, labeled HGF.
 The boundary line HG is known as solvus while boundary
line GF is known as solidus.

Fig: The copper–silver phase diagram.

 The horizontal line BEG, which is parallel to the composition axis and extends between the maximum solubility positions
for 𝜶 𝒂𝒏𝒅 𝜷 , may also be considered a solidus line.
 It represents the lowest temperature at which a liquid phase may exist for any copper–silver alloy that is at
equilibrium.
 Binary Eutectic Phase Diagram
The copper–silver Eutectic phase diagram
 There are also 3 two-phase regions for the Cu-Ag system i.e., 𝜶 + 𝑳, 𝜷 + 𝑳 𝒂𝒏𝒅 𝜶 + 𝜷
 Compositions and relative amounts for the phases may be
determined using tie lines and the lever rule as outlined
previously.
 The liquidus line AE and EF meet at point E, Eutectic point,
designated by composition CE and temperature TE.
 For the Cu –Ag system, CE and TE are 71.9 wt% Ag and
779℃ respectively.
 Eutectic reaction: upon cooling, a liquid phase is transformed
into the two solid 𝜶 and 𝜷 phases at the temperature TE; the
opposite reaction occurs upon heating.
 The horizontal solidus line at TE is called the eutectic
isotherm.
 Eutectic reaction occurs isothermally or at constant
temperature to yield to solid phases.

Fig: The copper–silver phase diagram.

 Binary Eutectic Phase Diagram
The Lead – Tin Eutectic phase diagram.

 The Pb – Sn phase diagram has a general shape similar to that

for Cu Ag.
 The eutectic point – CE = 61.9 wt%Sn and TE = 183 ℃.
 The low-melting-temperature alloys are prepared having
near-eutectic compositions.
 A familiar example is 60–40 solder, which contains 60
wt% Sn and 40 wt% Pb.
 An alloy of the above composition is completely molten
at about 185 ℃.
 The above makes this material (Alloy composition)
especially attractive as a low-temperature solder
because it is easily melted.
 Class work
 For a 40 wt% Sn–60 wt% Pb alloy at 150℃.
a. What phase(s) is (are) present?
b. What is (are) the composition(s) of the phase(s)?
c. Calculate the relative amount of each phase Fig: The Lead – Tin phase diagram.
present in terms of mass fraction.
 Binary Eutectic Phase Diagram
The Lead – TIn Eutectic phase diagram
 Solution

 For a 40 wt% Sn–60 wt% Pb alloy at 150oC.

a. What phase(s) is (are) present?
 Locate this temperature–composition point on the phase diagram
(point B). Since it is within the 𝜶 + 𝜷 region, both 𝜶 and 𝜷 phases
will coexist.
b. What is (are) the composition(s) of the phase(s)?
 Because two phases are present, it becomes necessary to construct
a tie line across the 𝜶 + 𝜷 phase field at 150℃, as indicated in
Figure. The composition of the 𝜶 phase is about 11 wt% Sn–89 wt%
Pb, denoted as C𝜶 while the composition for the 𝜷 phaseabout 98
wt% Sn–2 wt% Pb (C𝜷)
c. Calculate the relative amount of each phase
present in terms of mass fraction

𝐶 −𝐶 98 − 40
𝑊 = = = 0.67
𝐶 −𝐶 98 − 11 Fig: The lead–tin phase diagram showing a 40 wt% Sn–
60 wt% Pb alloy at 150oC (point B).
𝐶 −𝐶 40 − 11
𝑊 = = = 0.33
𝐶 −𝐶 98 − 11
 Development of Microstructure in Eutectic Alloys
 Depending on composition, several different types of microstructures are possible for the slow cooling of alloys
belonging to binary eutectic systems.
1. Compositions ranging between a pure component and the
max. solid solubility for that component at RT [20oC]
 For a Pb-Sn system, consider an alloy of composition C1 as it is
slowly cooled (along vertical line ww’) from a temperature Fig: Schematic
within the liquid-phase region, say, 350oC. representations
of the
 The alloy remains totally liquid and of composition C1 until we equilibrium
cross the liquidus line at approximately 330℃, at which time microstructures
for a lead–tin
the solid 𝜶 − phase begins to form. alloy of
composition C1
 With continued cooling, it goes through the narrow 𝜶 + 𝑳 as it is cooled
phase region and more of the solid 𝜶 forms. from the liquid-
phase region.
 The liquid- and solid 𝜶 -phase compositions are different,
which follow along the liquidus and solidus phase
boundaries, respectively.
 Solidification reaches completion at the point where line ww’
crosses the solidus line.
 The resulting alloy is polycrystalline with a uniform composition
of C1.
 No subsequent changes occur upon cooling to room temp.
 Development of Microstructure in Eutectic Alloys
2. Compositions that range between the room temperature solubility limit and the maximum solid
solubility at the eutectic temperature
 For a Pb – Sn system, these compositions extend from about 2
to 18.3 wt% Sn (for Pb-rich alloys) and from 97.8 to
approximately 99 wt% Sn (for Sn-rich alloys).
 Consider an alloy of composition C2 as it is cooled along the
Fig: Schematic
vertical line xx’. representations
of the
 The alloy remains totally liquid and of composition C2 until we equilibrium
cross the liquidus line at approximately 300℃, at which time microstructures
the solid 𝛼− phase begins to form. for a lead–tin
alloy of
 With continued cooling, it goes through the narrow 𝜶+𝑳 composition C2
as it is cooled
phase region and more of the solid 𝜶 forms. from the liquid-
phase region.
 Just above the solvus intersection, point f, the microstructure
consists of 𝜶(𝒂𝒍𝒑𝒉𝒂) grains of composition C2.
 Upon crossing the solvus line, the 𝜶 (𝒂𝒍𝒑𝒉𝒂) solid solubility is
exceeded, which results in the formation of small 𝜷-phase
particles in the microstructure insert at point g.
 With continued cooling, 𝜷-phase particles grow in size
because the mass fraction of the 𝜷-phase increases slightly
with decreasing temperature.
 Development of Microstructure in Eutectic Alloys
3. Solidification of the eutectic composition
 For a Pb – Sn system, consider solidification of the eutectic
composition, 61.9 wt% Sn (C3) along line yy’.
 As the temperature is lowered, no changes occur until we
reach the eutectic temperature, 183℃.
 Upon crossing the eutectic isotherm, the liquid transforms
into the two 𝜶 and 𝜷 phases.
 This transformation may be represented by the reaction

 During this transformation, there must be a redistribution

of the lead and tin components because the 𝜶 and 𝜷 phases
have different compositions different from the Liquid phase.
 This redistribution is accomplished by atomic diffusion.
 The microstructure of the solid that results from this
transformation (eutectic structure) consists of alternating
layers (sometimes called lamellae) of the 𝜶 and 𝜷 phases Fig: Schematic representations of the equilibrium
that form simultaneously during the transformation. microstructures for a lead–tin alloy of eutectic composition
C3 above and below the eutectic temp.
 Subsequent cooling of the alloy from just below the eutectic
to room temperature results in only minor microstructural
alterations.
 DEVELOPMENT OF MICROSTRUCTURE IN EUTECTIC ALLOYS
3. Solidification of the eutectic composition Cont’
Fig: Schematic
 The microstructural change that accompanies this representation of the
eutectic transformation shown in the figure.., which formation of the
shows the 𝜶 − 𝜷 layered eutectic growing into and eutectic structure for
the lead–tin system.
replacing the liquid phase. Directions of diffusion
 The process of the redistribution of lead and tin occurs of tin and lead atoms
are indicated by blue
by diffusion in the liquid just ahead of the eutectic–liquid and red arrows,
interface. respectively.
 The arrows indicate the directions of diffusion of lead
and tin atoms;
Fig. Photomicrograph
 Lead atoms diffuse toward the 𝜶- phase layers showing the
because this 𝜶- phase is lead-rich (18.3 wt% Sn – microstructure of a
81.7 wt% Pb); lead–tin alloy of
eutectic
 Tin atoms diffuse toward the 𝜷- phase layers
composition. This
because this 𝜷- phase is tin-rich (97.8 wt% Sn–2.2 microstructure
wt% Pb). consists of
alternating layers of a
 The eutectic structure forms in these alternating layers lead-rich 𝛼 −
because, for this lamellar configuration, atomic diffusion 𝑝ℎ𝑎𝑠𝑒 solid
of lead and tin need only occur over relatively short solution (dark layers),
distances. and a tin-rich 𝛽-phase
solid solution (light
layers)
 Development of Microstructure in Eutectic Alloys
4. System that includes all compositions other than the eutectic that, when cooled, cross
the eutectic isotherm.
 For a Pb – Sn system, consider an alloy of composition C4
as it is cooled along the vertical line zz’.
 The microstructural development between points j and l
is similar to that for the second case.
 Just above the eutectic line, the alpha (𝜶) and
liquid phases are present with compositions of
approximately 18.3 and 61.9 wt% Sn.
 As the temperature is lowered to just below the
eutectic, the remaining liquid phase, which is of the
eutectic composition, transforms into the eutectic
structure (i.e., alternating 𝜶 and 𝜷 lamellae).
 No significant changes occur with the 𝜶- phase that
formed during cooling through the 𝜶 + 𝑳 region (or
before eutectic line).
 Primary 𝜶 – refer to alpha phase formed prior to
crossing the eutectic isotherm.
Fig: Schematic representations of the equilibrium microstructures for a lead–
 Eutectic 𝜶 – refer to alpha found in the eutectic
tin alloy of composition C4 as it is cooled from the liquid-phase region
structure.
 Development of Microstructure in Eutectic Alloys
4. System that includes all compositions other than the eutectic that, when cooled, cross
the eutectic isotherm. Fig: Schematic
representation of
microstructure of a lead–
tin alloy of composition 40
wt% Sn–60 wt% Pb. This
microstructure is
composed of a primary
lead-rich 𝛼 − phase (large
dark regions) within a
lamellar eutectic structure
consisting of a tin-rich
𝛽 −phase (light layers) and
a lead-rich 𝛼 phase (dark
layers)

Fig: Photomicrograph showing the

microstructure of a lead–tin alloy
of composition 50 wt% Sn–50
wt% Pb. This microstructure is
Class work: composed of a primary lead-rich
𝛼 − phase (large dark regions)
 Compute
within a lamellar eutectic
 The fraction of the eutectic microconstituent. structure consisting of a tin-rich
 The fraction of primary 𝛼. 𝛽 −phase (light layers) and a lead-
 The fractions of total 𝛼, (both eutectic and rich 𝛼 phase (dark layers)
primary).
 The fractions of total 𝛽.
 Development of Microstructure in Eutectic Alloys
4. System that includes all compositions other than the eutectic that, when cooled, cross
the eutectic isotherm.
 Compute
 The fraction of the eutectic microconstituent.
𝑃 𝐶 − 18.3
𝑊 =𝑊 = =
𝑃 + 𝑄 61.9 − 18.3

 The fraction of primary 𝛼.

𝑄 61.9 − 𝐶
𝑊 = =
𝑃 + 𝑄 61.9 − 18.3

 The fractions of total 𝛼, (both eutectic and primary).

𝑄+𝑅 97.8 − 𝐶
𝑊 = =
𝑃 + 𝑄 + 𝑅 97.8 − 18.3

 The fractions of total 𝛽.

𝑃 𝐶 − 18.3
𝑊 = =
𝑃 + 𝑄 + 𝑅 97.8 − 18.3
 Equilibrium Diagrams having Intermediate phases or compounds
 Examples: copper–zinc system, magnesium–lead system.
 For some systems, discrete intermediate compounds rather than solid solutions may be found on the phase diagram,
and these compounds have distinct chemical formulas; for metal–metal systems, they are called intermetallic
compounds.

 For example, consider the magnesium–lead

system.
 The compound Mg2Pb has a composition
of 19 wt% Mg–81 wt% Pb and is
represented as a vertical line on the
diagram, rather than as a phase region
of finite width; hence, Mg2Pb can exist
by itself only at this precise
composition.

The magnesium – lead phase diagram.

 Eutectoid and Peritectic Reactions
 Apart from the eutectic point, there are other invariants points involving three different phases at equilibrium found
for some alloy systems.
 Eutectoid point
o Characterized by a eutectoid reaction (Eutectic like).
o The feature distinguishing eutectoid from eutectic is that one solid phase instead of a liquid transforms
into two other solid phases at a single temperature.
o A eutectoid reaction found in the iron–carbon system is very important in the heat treating of steels.
o For a copper–zinc system, at 560℃ and 74 wt% Zn–26 wt% C, upon cooling 𝜹 −solid phase transforms into
two other solid phases (𝜸 𝒂𝒏𝒅 𝝐) according to the reaction.

 Peritectic point
o Characterized by a peritectic reaction (Eutectic like).
o Upon heating, one solid phase transforms into a liquid phase and another solid phase.
o A peritectic exists for the copper–zinc system , (point P) at 598 ℃ and 78.6 wt% Zn–21.4 wt% Cu; this
reaction is as follows:
 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+𝑭=𝑪+𝑵
Where:
 P is the number of phases present.
 F is 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. Q
 F can also defined as the number of variables that can be
changed independently without altering the number of phases
that coexist at equilibrium.
 C represents the number of components in the system i.e., in
the case of phase diagrams, are the materials at the two
extremes of the horizontal compositional axis.
 N is the number of non-compositional variables (e.g.,
temperature and pressure).
 Consider a copper – silver system
 Because pressure is constant (1 atm), the
parameter N = 1 since temperature is the only
remaining non-compositional variable.
 The number of components C = 2 (namely, Cu and
Ag)
 For a single phase region (e.g., 𝜶 − 𝒑𝒉𝒂𝒔𝒆), P = 1, thus…….. 1 + 𝐹 = 2 + 1 𝐹=2
o 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
o For example point Q can be described as: Composition = 5wt%Ag and Temperature= 800oC
 THE GIBBS PHASE RULE
 For a two- phase region (e.g, 𝜶 + 𝑳 𝒑𝒉𝒂𝒔𝒆), P = 2, thus……..
2+𝐹 = 2+1 𝐹=1
o This means that we need to specify either temperature or the
composition of one of the phases to completely define the system.
o For example, suppose that we decide to specify temperature for the
𝜶 + 𝑳 𝒑𝒉𝒂𝒔𝒆 region, say, T1 as in the Figure.
 The compositions of the 𝜶 and liquid phases (C𝜶 and CL) are thus
dictated by the extremes of the tie line constructed at T1 across
the 𝜶 + 𝑳 field.
o If we specified the composition, say C𝜶;
 Then both the temperature of the alloy (T1) and the composition
of the liquid phase (CL) are established, again by the tie line
drawn across the 𝜶 + 𝑳 phase field so as to give this C𝜶
composition.
 For a three- phase region (e.g, Eutectic point), P = 3, thus……..
3+𝐹 = 2+1 𝐹=0
o This means that the compositions of all three phases—as well as the
temperature—are fixed (No degree of freedom).
o For example, for Cu-Ag system, the eutectic point is fixed. At this
point,
 Temperature is 779oC
 Three phases are in equilibrium :
 the composition 𝛼 -phase is fixed at 8.0 wt% Ag,
 The composition of the liquid is fixed at 71.9 wt% Ag,
 The composition of the 𝜷 − 𝒑𝒉𝒂𝒔𝒆 is fixed at 91.2 wt% Ag.
 THE IRON–CARBON SYSTEM
 Of all binary alloy systems, the one that is possibly the most important is that for iron and carbon.
 Both steels and cast irons are essentially iron–carbon alloys.
The Fe – Fe3C phase diagram
 The iron–carbon system may be divided into two
parts: an iron-rich portion and Carbon rich
portion(pure graphite)(6.70 - 100 wt% C)- not
shown!
 The left vertical axis
 Has pure Iron.
 Pure iron exist inform of 𝜶 -ferrite (BCC)
room temperature up to 912oC.
 At 912oC, ferrite changes to austenite
(FCC). This austenite persist up to 1394oC
 At 1394oC, austenite changes to 𝜹-ferrite
(BCC) which finally melts at 1538oC.
 The composition axis
 Extends only to 6.70 wt% C.
 At this concentration the intermediate
compound iron carbide or cementite
(Fe3C), is formed.
 The intermediate compound Fe3C is
represented by the right vertical line/axis.
 In practice, all steels and cast irons have
carbon contents less than 6.70 wt% C;
therefore, we consider only the iron–iron
carbide system. Fig: The Iron– Carbon phase diagram.
 The Fe – Fe3C phase diagram
 Carbon is an interstitial impurity in iron and forms a solid solution with each of 𝜶 − 𝒇𝒆𝒓𝒓𝒊𝒕𝒆, 𝜸 − 𝐚𝐮𝐬𝐭𝐞𝐧𝐢𝐭𝐞 and 𝜹 −
𝒇𝒆𝒓𝒓𝒊𝒕𝒆.

𝜶 −𝒇𝒆𝒓𝒓𝒊𝒕𝒆 𝛄 − 𝒂𝒖𝒔𝒕𝒆𝒏𝒊𝒕𝒆
 It is solid solution of C in BCC Fe  This phase (if it contain only C as the alloying element) is not
 Has BCC crystal structure. stable at temperatures below 727oC.
 Stable at room temperature.  Has an FCC crystal structure
 The maximum solubility of C in 𝛼 − 𝑓𝑒𝑟𝑟𝑖𝑡𝑒  The maximum solubility of carbon in austenite, 2.14 wt%, occurs
of 0.022 wt% at 727oC. at 1147oC.
 The limited solubility is explained by the  This solubility is approximately 100 times greater than the
shape and size of the BCC interstitial maximum for BCC ferrite because the FCC octahedral sites are
positions (BCC-tetrahedral sites), which larger than the BCC tetrahedral sites.
make it difficult to accommodate more  Phase transformations involving austenite are very important in
carbon atoms. the heat treating of steels.
 Nevertheless, carbon significantly  Austenite is nonmagnetic.
influences the mechanical properties of  Austenite transforms to BCC δ-ferrite at 1395 °C
ferrite.
 The 𝛼 − 𝑓𝑒𝑟𝑟𝑖𝑡𝑒 phase is relatively soft, 𝛅 − 𝒇𝒆𝒓𝒓𝒊𝒕𝒆
may be made magnetic at temperatures  This phase is virtually the same as 𝛼 − 𝑓𝑒𝑟𝑟𝑖𝑡𝑒 , except for the
below 768oC. range of temperatures over which each exists.
 Transforms to FCC γ-austenite at 912 °C.  Also has a BCC crystal structure.
 Because the 𝛿 − 𝑓𝑒𝑟𝑟𝑖𝑡𝑒 is stable only at relatively high
temperatures, (above 1394 °C )it is of no technological
importance.
 Melts at 1538 °C
 The Fe – Fe3C phase diagram
Cementite, Fe3C Classification of ferrous alloys
 Cementite is formed when the solubility limit of  Ferrous alloys are those in which iron is the prime
carbon in 𝛼-ferrite is exceeded below 727oC. component, but carbon as well as other alloying elements
may be present.
 Cementite also coexists with the 𝛾 − phase
 Ferrous alloys are classified based on carbon content,
between 727oC and 1147oC. there are three types: iron, steel, and cast iron.
 Cementite is very hard and brittle;  Pure Iron
 The strength of some steels is greatly enhanced o Contain less than 0.008 wt% C.
by its presence. o Composed almost exclusively of the ferrite
 Cementite is only metastable; that is, it remains phase at room temperature.
as a compound indefinitely at room temperature.  Steels
o However, if heated to between 650oC and o Contain between 0.008 and 2.14 wt% C.
o In most steels, the microstructure consists of
700oC for several years, it gradually changes
both 𝜶 − 𝒇𝒆𝒓𝒓𝒊𝒕𝒆 and Fe3C phases.
or transforms into 𝛼 -iron and carbon, in the o Although a steel alloy may contain as much as
form of graphite. 2.14 wt% C, in practice, carbon concentrations
 However, because the decomposition rate of rarely exceed 1.0 wt%.
cementite is extremely sluggish, virtually all the o Plain carbon steels: carbon is the main alloy
carbon in steel is as Fe3C instead of graphite. element.
 Addition of silicon to cast irons greatly o Alloy steels: contain appreciable
accelerates the cementite decomposition reaction concentrations of other elements.
 Cast Irons
to form graphite.
o Contain between 2.14 and 6.70 wt% C.
o However, commercial cast irons normally
contain less than 4.5 wt% C.
 The Fe – Fe3C phase diagram

Invariant reactions

 Eutectic reaction: At 4.30 wt% C and 1147oC

 Eutectoid reaction: At 0.76 wt%C and 727oC

 Peritectic reaction: 0.16%C at 1495oC

+ →
Development of Microstructure in Iron - Carbon alloys
 Development of Microstructure in Iron - Carbon alloys
 The microstructure formed depends on composition (carbon content) and heat treatment.
 We will consider very slow cooling of steel alloys, in which equilibrium is continuously maintained
Eutectoid Steel
 Consider an alloy of eutectoid composition (0.76 wt% C) as it is cooled
from a temperature within the 𝛾-phase region, say 800oC (point a).
 Initially, the alloy is composed entirely of the austenite phase having a
composition of 0.76 wt% C.
 As the alloy is cooled, no changes occur until the eutectoid temperature
(727oC) is reached.
 Upon crossing this temperature to point b, the austenite transforms
according to Equation below:

 The resulting microstructure, pearlite, consists of alternating layers or

lamellae of the two phases : 𝜶-ferrite and cementite( Fe3C) that form
simultaneously.
 The layers of alternating phases in pearlite are formed for the same
reason as layered structure of eutectic structures i.e,
 By redistribution C atoms between ferrite (0.022 wt%) and
cementite (6.7 wt%) by atomic diffusion.
 Subsequent cooling of the pearlite from point b produces relatively
insignificant microstructural changes.
 Mechanically, pearlite has properties intermediate between those of the
soft, ductile ferrite and the hard, brittle cementite.
 Development of Microstructure in Iron - Carbon alloys
Eutectoid Steel
 Carbon atoms diffuse away from the 0.022-wt% ferrite regions and to the 6.70-wt% cementite
layers, as the pearlite extends from the grain boundary into the unreacted austenite grain.
 The layered pearlite forms because carbon atoms need diffuse only minimal distances with the
formation of this structure.

The relative layer thickness

is approximately 8 to 1

Fig: Photomicrograph of a eutectoid steel showing the

pearlite microstructure consisting of alternating
layers of 𝜶-ferrite (the light phase) and Fe3C (thin Fig: Schematic representation of the formation of
layers most of which appear dark). pearlite from austenite; direction of carbon diffusion
indicated by arrows.
 Development of Microstructure in Iron - Carbon alloys
Hypoeutectoid Steel (less than eutectoid)
 Consider a composition C0 to the left of the eutectoid, between
0.022 and 0.76 wt% C.
 Cooling an alloy of this composition is represented by moving down
the vertical line yy’.
 At about 875oC, point c, the microstructure consists entirely of
grains of the 𝜸 − phase.
 In cooling to point d, about 775oC, which is within the 𝜶 + 𝜸 phase
region, both these phases coexist.
 Most of the small a particles form along the original 𝜸 grain
boundaries.
 Cooling from point d to e, just above the eutectoid but still in the
𝜶 + 𝜸 region, produces an increased fraction of the 𝜶 phase.
 At this point, the compositions of the:
 𝜶 − 𝒑𝒉𝒂𝒔𝒆 is 0.022 wt% C while that of the
 𝜸 − 𝒑𝒉𝒂𝒔𝒆 is is of the eutectoid composition, 0.76 wt% C.

 Cooling to below the eutectoid, to point f, all of the remaining 𝜸 −

𝒑𝒉𝒂𝒔𝒆 (having the eutectoid composition) transforms into pearlite
according to the equation below:
 Development of Microstructure in Iron - Carbon alloys
Hypoeutectoid Steel (less than eutectoid)
 There is virtually no change in the 𝜶- phase that existed
before crossing the eutectoid temperature.
 Thus the ferrite phase is present both in the:
 Pearlite – the ferrite in pearlite is known as eutectoid
ferrite.
 Phase that formed while cooling through the 𝜶 +
𝜸 phase region before the eutectoid temperature.
o This ferrite phase is known as pro-eutectoid
ferrite.
 Pro-eutectoid ferrite is normally present as a continuous Fig: Photomicrograph of a 0.38 wt% C steel having a
microstructure consisting of pearlite and proeutectoid ferrite.
matrix phase surrounding the isolated pearlite colonies.
 Note: There are two microconstituents present in a
hypoeutectoid steel that is slowly cooled to room below the
eutectoid temperature:
 Proeutectoid ferrite
 Pearlite (eutectoid ferrite + cementite)
 Development of Microstructure in Iron - Carbon alloys
Hypoeutectoid Steel (less than eutectoid)
Determining the relative amounts of proeutectoid ferrite and pearlite

Application of the lever rule with tie line that extends from the:
Eutectoid composition (0.76 wt% C) to 𝜶 – (𝜶 + Fe3C) boundary
(0.022 wt% C).
𝑻 𝑪,𝟎 𝟎.𝟎𝟐𝟐
 Fraction of pearlite, 𝑾𝒑 = =
𝑻 𝑼 𝟎.𝟕𝟔 𝟎.𝟎𝟐𝟐

𝑼 𝟎.𝟕𝟔 𝑪,𝟎
 Fraction of proeutectoid 𝜶, 𝑾𝜶 = =
𝑻 𝑼 𝟎.𝟕𝟔 𝟎.𝟎𝟐𝟐

 Fraction of total ferrite(eutectoid and proeutectoid)

𝑼 𝑿 𝟔.𝟕 𝑪,𝟎
𝑾𝜶𝑻 = =
𝑻 𝑼 𝑿 𝟔.𝟕 𝟎.𝟎𝟐𝟐

𝑻 𝑪,𝟎 𝟎.𝟎𝟐𝟐
 Fraction of cementite, 𝑾𝑪 = =
𝑻 𝑼 𝑿 𝟔.𝟕 𝟎.𝟎𝟐𝟐
 Development of Microstructure in Iron - Carbon alloys
Hyper-eutectoid Steel (more than eutectoid)
 Consider a composition C1 to the right of the eutectoid,
between 0.76 wt% C and 2.14 wt%C cooled from Temp in the
𝜸 − phase.
 Cooling an alloy of this composition is represented by moving
down the vertical line zz’.
 At point g, the microstructure consists entirely of grains of
the 𝜸 − phase with the composition C1.
 In cooling to point h which is within the 𝜸 + 𝑭𝒆𝟑 𝑪 phase
region, both these phases coexist.
 The cementite phase begins to form along the initial 𝜸 grain
boundaries.
 This cementite is called proeutectoid cementite—that
which forms before the eutectoid reaction.
 Cooling through the eutectoid to point i, all remaining austenite
of eutectoid composition is converted into pearlite;
 Thus, the resulting microstructure consists of pearlite and
proeutectoid cementite as microconstituents
Development of Microstructure in Iron - Carbon alloys
Hyper-eutectoid Steel (more than eutectoid)

Fig: Photomicrograph of a 1.4 wt% C steel having a

microstructure consisting of a white proeutectoid
cementite network surrounding the pearlite colonies.
 Development of Microstructure in Iron - Carbon alloys
Hyper-eutectoid Steel (more than eutectoid)
Determining the relative amounts of proeutectoid cementite (Fe3C) and pearlite
Application of the lever rule with tie line that extends from the:
 Eutectoid composition (0.76 wt% C) to (𝜶 + Fe3C) – Fe3C
boundary (6.7 wt% C)
,
.
 Fraction of pearlite, 𝑾𝒑 = =
. .

,
.
 Fraction of proeutectoid Fe3C, 𝑾𝑪 = =
. .

 Fraction of total cementite (eutectoid and proeutectoid)

𝑸 𝑹 𝑪,𝟏 𝟎.𝟎𝟐𝟐
𝑾𝑪𝑻 = =
𝑸 𝑹 𝑺 𝟔.𝟕 𝟎.𝟎𝟐𝟐

𝑺 𝟔.𝟕 𝑪,
 Fraction of ferrite, 𝑾𝜶 = = 𝟏
𝑻 𝑼 𝑿 𝟔.𝟕 𝟎.𝟎𝟐𝟐
 Development of Microstructure in Iron - Carbon alloys
Class work
1. For a 99.65 wt% Fe–0.35 wt% C alloy at a temperature just below the eutectoid, determine the
following:
(a) The fractions of total ferrite and cementite phases (Ans: 0.95, 0.05)
(b) The fractions of the proeutectoid ferrite and pearlite (Ans: 0.56, 0.44)
(c) The fraction of eutectoid ferrite (Ans: 0.39)
(d) Consider 4Kg of austenite containing 0.35wt%C, how many kilograms of each of the phases
in (a), (b) and (c) are formed?
2. Consider 1.0 kg of austenite containing 1.15 wt% C, cooled to below 727°C (1341°F).
a) What is the pro-eutectoid phase?
b) How many kilograms each of total ferrite and cementite form? (0.83 kg, 0.17 kg)
c) How many kilograms each of pearlite and the pro-eutectoid phase form? (0.93 kg, 0.07 kg)
d) Schematically sketch and label the resulting microstructure.
Thank You !!