Solidification and Phase

Diagrams

Dr. Siddhalingeshwar I.G.

 Unit II

Chapter 4: Solidification and phase diagrams:

Mechanism of solidification, Homogeneous and heterogeneous nucleation, crystal
growth, cast metal structures, Solid solutions, Hume Rothery rules, substitutional
07
and interstitial solid solutions, intermediate phases, Gibbs phase rule, construction
hours
of equilibrium diagrams, equilibrium diagrams involving complete and partial
solubility, lever rule, Iron carbon equilibrium diagram, description of phases,
solidification of steels and cast irons, invariant reactions, Numericals.
Chapter 5: Ferrous and Non ferrous materials:
06
Properties, composition and uses of cast irons and steels, AISI and BIS designation
hours
of steels. Aluminum, Magnesium and Titanium alloys.
Chapter 6: Heat treatment of metals:
Objectives, Annealing and its types, normalizing, hardening, tempering,
austempering, martempering, hardenability, surface hardening methods like 06
carburizing, cyaniding, nitriding, flame hardening and induction hardening; Age hours
hardening of Aluminum -Copper alloys. Time-temperature-transformation (TTT)
curves, continuous cooling curves.

2
 Chapter 4: Lesson Schedule

01. Solid solutions, types of solid solutions, Hume Rothery Rules for complete miscibility.

02. Gibb’s phase rule and its applications.

03. Cooling curves for pure metal, binary solid solution.
04. Binary phase diagrams involving complete and partial solubility.
05. Examples on phase diagram and numerical.
06. Iron-Carbon (Fe-Fe3 C) equilibrium diagram in detail with emphasis on
invariant reactions.
07. Microstructure of slowly cooled steels, effect of alloying elements on
the Fe-C diagram.

3
The understanding of Science of Solidification is important because it is
applied to a wide range of materials from metals and alloys to ceramics to
polymers. Solidification is of such importance simply because one of its major
practical applications, namely casting, is a very economic method of forming a
component. Properties of casting are not easy to control, hence this
understanding is important to manipulate the process to achieve desired
results.

4
The understanding of phase diagrams for alloy systems is extremely important
because there is a strong correlation between microstructure and mechanical
properties, and the development of microstructure of an alloy is related to the
characteristics of its phase diagram.

In addition, phase diagrams provide valuable information about melting,

casting, crystallization, and other phenomena.

5
 Learning Outcomes

Explain the mechanism of solidification in pure metals and alloys and

Distinguish between homogeneous and heterogeneous nucleation.

Calculate critical radius, number of nuclei and driving force for homogeneous

nucleation.

Utilize the Gibbs Phase Rule to compute equilibrium number of phases for any

given temperature, pressure and number of independent components.

Construct a phase diagram from phase composition data as well as from cooling

curves.

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 Learning Outcomes

Given a binary phase diagram, the composition of alloy, its temperature and

assuming that the alloy is at equilibrium, compute what phases are present, the
composition of the phases, the mass fraction of phases and comment on the
solidification phenomenon.
Identify the important phase regions of the Fe-C phase diagram.
Describe the significance of critical cooling rate and explain the factors affecting it.

Explain the various micro constituents of Iron and Steel, their microstructure,

characterization, properties and areas of application.

Explain the transformations that take place in the structure of steels and cast

iron, and identify the associated microstructure.

7
Why is solidification important?

80% of ALL industry involves a casting or solidification process of a material in

various ways;

The initial microstructure of the material forms during the casting or

solidification process where the melted alloy becomes a (crystalline) solid;

During the last century, by examining metal alloys with an optical microscope

after polishing and etching the surface, it was discovered that the

microstructures influenced the material's properties .

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9
Classification

10
 Why does anything solidify?

 The energy of the crystal structure is less than that of the liquid

 The difference is the volume free energy DGv

 As the solid grows in size, the magnitude of the total volume free

energy increases…
 But it is a negative value.

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 When solids form in a liquid there is an interface created

 The surface free energy, s is associated with this interface

 As the solid grows, the total surface free energy increases, and….

 It’s a positive value.

 The total change in free energy for the system is the sum of the two factors.

 DG = 4/3 π r 3DGv + 4 π r 2s

 The volume free energy goes up as the cube of the radius.

 The surface free energy goes up as the square of the radius.

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Schematic Representation of Solidification

13
 Formation of Nuclei

 Molecules are always bumping into each other – sometimes they

stick
 At lower kinetic energies more stick

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15
Homogeneous nucleation
Gibbs free energy
 Energies involved in Homogeneous nucleation

The total free energy of the solid-liquid system changes with the size of the solid.
The solid is an embryo if its radius is less than the critical radius, and is a nucleus if its
radius is greater than the critical radius 18
An interface is created when a solid forms from the liquid
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Dendritic  Structure at the Solid-Liquid
Interface of a  Ni-Based Single Crystal

Microstructure of rolled and annealed brass

(400X magnification) 20
A solid forming on an impurity can assumed the critical radius with a smaller increase in the
surface energy.
Thus, heterogeneous nucleation can occur with relatively low undercoolings.
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Nucleation in solids. Heterogeneous nucleation can take place at defects like
dislocations, grain boundaries, interphase interfaces and free surfaces. Homogeneous
nucleation, in defect-free regions, is rare.

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 Grain Size

 Solidification caused by homogeneous nucleation occurs suddenly,

and only produces a few grains.
 In heterogeneous nucleation, solidification occurs on many “seeds”,
so the grains are smaller, and more uniform.

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 Growth and Solidification

 If a melt is cooled slowly, and the temperature is the same

throughout, solidification occurs with equal probability everywhere in
the melt. However….
 Metals are usually cooled from the container walls – so solidification
starts on the walls.

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 Cooling Curves

 Pouring Temperature.

 Superheat – the difference between the pouring temperature and the

freezing temperature.
 Thermal arrest – constant temperature region on the cooling curve.

 Total solidification time – the time it takes to solidify, from the time you pour
the mold.
 Local solidification time – time to remove the latent heat.

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 Cooling Curve

Pouring Temperature

Superheat
Temperature

Local Solidification Time

Total Solidification Time

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Solidification of pure metals
Solid solutions

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 Solid solutions- Hume-Rothery rules

 The Hume-Rothery rules, named after William Hume-Rothery, are a set

of basic rules describing the conditions under which an element could
dissolve in a metal, forming a solid solution. There are two sets of rules, one
which refers to substitutional solid solutions, and another which refers to
interstitial solid solutions.

For interstitial solid solutions, the Hume-Rothery rules are:

1. Solute atoms must be smaller than the interstitial sites in the solvent lattice.

2. The solute and solvent should have similar electronegativity.

31
 Dr. William Hume-Rothery

The youthful Hume-Rothery read chemistry at Oxford with distinction despite his
disability and then worked for his PhD at the Royal School of Mines in London. Upon
his return to Oxford with a newly found enthusiasm for work on alloys, he was given
a little bench space in the Dyson-Perrins laboratory. In cramped accommodation, he
began the long series of investigations into alloy equilibria and the inspired
hypotheses which led to the famous Hume-Rothery Rules. 

32
 Hume-Rothery rules

For substitutional solid solutions, the Hume-Rothery rules are:

1. The atomic radii of the solute and solvent atoms must differ by no more than
15%.

2. The crystal structures of solute and solvent must match.

3. Complete solubility occurs when the solvent and solute have the same
valency. A metal will dissolve a metal of higher valency to a greater extent
than one of lower valency.

4. The solute and solvent should have similar electronegativity. If the

electronegativity difference is too great, the metals will tend to form
intermetallic compounds instead of solid solutions. 33
•An example of a substitutional solid solution is found for copper and nickel.
These two elements are completely soluble in one another at all proportions.
• With regard to the aforementioned rules that govern degree of solubility, the

atomic radii for copper and nickel are 0.128 and 0.125 nm, respectively,
•both have the FCC crystal structure, and

•their electronegativities are 1.9 and 1.8 ;

•finally, the most common valences are +1 for copper (although it sometimes

can be + 2) and +2 for nickel.

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35
 For interstitial solid solutions, impurity atoms fill the voids or interstices among
the host atoms. For metallic materials that have relatively high atomic packing
factors, these interstitial positions are relatively small. Consequently, the atomic
diameter of an interstitial impurity must be substantially smaller than that of the
host atoms.
 Carbon forms an interstitial solid solution when added to iron; the maximum
concentration of carbon is about 2%.

 The atomic radius of the carbon atom is much less than that for iron: 0.071 nm

versus 0.124 nm.

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A solid solution is formed when two metals are completely soluble in liquid
state and also completely soluble in solid state. In other words, when
homogeneous mixtures of two or more kinds of atoms (of metals) occur in the

solid state, they are known as solid solutions.

The more abundant atomic form is referred as solvent and the less abundant
atomic form is referred as solute.

For example sterling silver (92.5 percent silver and the remainder copper) is a
solid solution of silver and copper.

Another example is brass. Brass is a solid solution of copper (64 percent) and
zinc (36 percent). In this case copper atoms are solvent atoms whereas zinc
atoms are solute atoms
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Substitutional Solid Solutions:
If the atoms of the solvent or parent metal are replaced in the crystal lattice
by atoms of the solute metal then the solid solution is known as substitutional
solid solution.

For example, copper atoms may substitute for nickel atoms without
disturbing the F.C.C. structure of nickel. In the substitutional solid solutions,
the substitution can be either disordered or ordered.

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39
In interstitial solid solutions, the solute atom does not displace a solvent
atom, but rather it enters one of the holes or interstices between the solvent
atoms.

An excellent example is iron-carbon system. In this system the carbon (solute
atom) atom occupies an interstitial position between iron (solvent atom) atoms.

 Normally, atoms which have atomic radii less than one angstrom are likely to
form interstitial solid solutions. Examples are atoms of carbon (0.77 A°), nitrogen
(0.71 A°), hydrogen (0.46 A°), Oxygen (0.60 A°) etc.

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41
 Two types of alloys:

 Substitutional: atoms of metals are about the same size and

replace each other in metal crystal

 Interstitial: atoms of different size. Smaller atoms fit into the

spaces between the larger atoms.
Phase diagrams
 Concepts

 Phase: A homogenous portion of a system that has uniform physical

and chemical characteristics.

 Solubility limit: Maximum concentration of solute atoms that may

dissolve in the solvent to form a solid solution.

 It depends on temperature.

 Solubility limit at some temperature is the composition that

corresponds to the intersection of the given temperature
coordinate and the solubility limit line.

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 Concepts (Cont.)

 Examples of phases: Pure material, gas, liquid, or solid solutions,

water and ice together (two phases), two polymorphic forms of a
solid, e.g., FCC & BCC (two phases).

 Heterogeneous systems: Systems consisting of two or more phases.

 Microstructure (in metals) is characterized by: Number of phases

present, their proportions, manner in which they are distributed or
arranged.

 Microstructure in alloys depends on alloying element present, their

concentrations, and heat treatment.

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 Concepts (Cont.)

 Phase equilibrium: A system is at equilibrium if its free energy is at a

minimum under some specified combination of temperature, pressure,
and composition, i.e., system characteristics do not change with time.

 Free energy: It is a function of the internal energy of a system. It is also a

function of the randomness or disorder of the atoms or molecules
(entropy).

 A change in temperature, pressure, and/or composition for a system in

equilibrium results in an increase in the free energy and in possible
spontaneous change to another state where free energy is lowered.

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 Gibbs' phase rule

Gibbs' phase rule was proposed by Josiah Willard Gibbs in the 1870s as the
equality
F=C-P+2
where P is the number of phases in thermodynamic equilibrium with each
other and C is the number of components.

Typical phases are solids, liquids and gases. A system involving one pure
chemical is an example of a one-component system. Two-component systems,
such as mixtures of water and ethanol, have two chemically independent
components.

F is the number of degrees of freedom, which means the number of intensive

properties such as temperature or pressure, which are independent of other
intensive variables.
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 Josiah Willard Gibbs

The publication of the paper "On the Equilibrium of Heterogeneous Substances"

(1874–78) is regarded as a landmark in the development of physical chemistry. In it,
Gibbs developed a rigorous mathematical theory for various transport phenomena,
including adsorption, electrochemistry, and the Marangoni effect in fluid
mixtures. He also formulated the phase rule. Awareness of this rule led to the
widespread use of phase diagrams by chemists.
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 Equilibrium phase diagram

 Phase diagram: Equilibrium or constitutional diagrams: It

represents the relationships between temperature and the
compositions and the quantities of phases at equilibrium.
 Phase diagrams for binary alloy (contains two components) is the
simplest.
 External pressure is assumed constant (atmospheric pressure).

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 Unary phase diagram
Pressure-temperature diagram for Water
The simplest phase diagrams are pressure-temperature diagrams of a
single simple substance, such as water.
The axes correspond to the pressure and temperature.
The phase diagram shows, in pressure-temperature space, the lines of
equilibrium or phase boundaries between the three phases of solid,
liquid, and gas.
Three externally controllable parameters that will affect phase
structure: temperature, pressure, and composition
The simplest type of phase diagram to understand is that for a one-
component system, in which composition is held constant
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51
Unary phasediagram

52
 Ex: Phase Diagram: Water-Sugar System

10 0
Solubility
80 Limit L

Temperature (°C)
Question: What is the (liquid)
60 +
L
solubility limit at 20C? (liquid solution S
40
i.e., syrup) (solid
Answer: 65wt% sugar. 20 sugar)

If Co < 65wt% sugar: sugar 0 20 40 6 065 8 0 10 0

C o =Composition (wt% sugar)

Water

Sugar
Pure

Pure
If Co > 65wt% sugar: syrup + sugar.

• Solubility limit increases with T: e.g., if T = 100C,

solubility limit = 80wt% sugar.

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 • Changing T can change # of phases: path A to B.
• Changing Co can change # of phases: path B to D.
B (100,70) D(100,90)
1 phase 2 phases
10 0

80 L
(liquid)
Temperature (°C)

• water- sugar 60 +
L S
system (liquid solution
40 (solid
i.e., syrup) sugar)
20 A(70, 20 )
2 phases
0
0 20 40 60 70 80 10 0
C o =Composition (wt% sugar)
54
 Binary isomorphous systems

 Example: Copper-Nickel phase diagram

 Isomorphous: Complete liquid and solid solubility of the components.
 Three different fields (delimited by phase boundary lines):
 Solid
 Liquid
 Solid + liquid

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 Binary isomorphous systems (Cont.)

 Nomenclature:
 For metallic alloys, solid solutions are designated by lowercase Greek
letters.
 Liquidus line.
 Solidus line.
 Thermal arrest occurs at the melting temperature of the pure metal
(liquidus and solidus lines intersect).

 For any composition other than pure components, melting occur over a
temperature range (between liquidus and solidus line). Both solids and
liquid phases are in equilibrium in this temperature range.

56
 Interpretation of phase diagrams

 Available information from phase diagrams:

 Present phases.
 Phase composition.
 Percentage (or fractions) of each phase.
 Determination of phases present: Locate the temperature-composition point
on the phase diagram and note the phase(s) with which the corresponding
phase field is labeled.

 Determination of phase composition:

 Locate temperature-composition point on the phase diagram.
 If one phase is present: phase composition is the given alloy
composition.
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 Two Component (Binary) Phase Diagram for
completely soluble elements or compounds

Melting
Liquid Temperature of A
Temperature, °C

Liquid +
Solid a

Solid a
Components
Melting Temperature of B
Percent A by weight 0 10 20 30 40 50 60 70 80 90 100
Percent B by weight 100 90 80 70 60 50 40 30 20 10 0
 Two Component (Binary) Phase Diagram: Ni - Cu

1700
Nickel - Copper Alloy
1600
Liquid Liquidus Line
1500
Temperature, °C

1455°C
1400

1300
Liquid +
1200 Solid a

1100 Solidus Line Solid a

1084°C
1000
Percent Ni by weight 0 10 20 30 40 50 60 70 80 90 100
Percent Cu by weight 100 90 80 70 60 50 40 30 20 10 0
 Binary Phase Diagram for
insoluble elements or compounds

Liquid A + B
Temperature. °C

Liquid + A
Liquid + B

Solid A + B

Composition of A
Composition of B

Actual atomic form will depend

on the composition of formation
 (1) Number and types of phases

• Rule 1: If we know T and Co, then we know:

--the # and types of phases present.
T(°C)
160 0

150 0 L (liquid)
i d us Cu-Ni phase
u

B(1250,35)
140 0 liq us diagram
l id
so
130 0 +  
• Examples: L (FCC solid
120 0 solution)
A(1100, 60):
1 phase:  110 0 A(1100,60)

B(1250, 35): 100 0

2 phases: L + 
0 20 40 60 80 10 0 wt% Ni

61
 Interpretation of phase diagrams (Cont.)

 Determination of phase composition if two phases are present:

 A tie line (isotherm) is constructed across the two-phase region at

the temperature of the alloy (it terminates at the phase boundary
lines on either side).

 The intersections of the tie line and the phase boundaries on either
side are noted.

 Perpendiculars are dropped from these intersections to the

horizontal composition axis, from which the composition of each of
the respective phases is read
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 (2) Composition of phases

• Rule 2: If we know T and Co, then we know:

--the composition of each phase.
Cu-Ni system
• Examples: T(°C)
C o = 35wt%Ni A
TA tie line us
At T A: u id
130 0 L (liquid) liq
Only Liquid (L) 
C L = C o ( = 35wt% Ni) L us+
B d
At T D: TB soli
Only Solid ( )  
C  = C o ( = 35wt% Ni ) 120 0 L+ D (solid)
At T B : TD
Both  and L 20 3 032 35 4 0 43 50
C L = C liquidus ( = 32wt% Ni here) C LC o C  wt% Ni
C  = C solidus ( = 43wt% Ni here)
63
 Interpretation of phase diagrams (Cont.)

 Determination of phase amounts (if more than one

phase):
 Construct a tie line.
 Locate the overall alloy composition on the tie line.
 Use lever rule (Line segment lengths may be determined
by direct measurement from phase diagram or by
subtracting compositions as taken from composition axis).
 WL = S / (R + S)
 W = R / (R + S)

64
 The Lever Rule

• Sum of weight fractions: WL  W  1

• Conservation of mass (Ni): C o  WLCL  W C 
• Combine above equations:
 C  Co  S C o  CL  R
WL W 
C   CL R  S C   CL R  S
• A geometric interpretation:
Co moment equilibrium:
CL C
WLR  WS
R S

WL W 1  W
solving gives Lever Rule
65
 (3) Weight fractions of phases

• Rule 3: If we know T and Co, then we know:

--the amount of each phase (given in wt%).
Cu-Ni system
• Examples: T(°C)
C o = 35wt%Ni
At T A: Only Liquid (L) TA A
tie line us
u id
WL = 100wt%, W  = 0 130 0 L (liquid) liq
At T D: Only Solid ( ) + 
B L
o li dus
WL = 0, W  = 100wt% TB R S
s
At T B : Both  and L 
120 0 L + 
S 43  35 D (solid)
WL     73 wt % TD
R S 43  32
20 3 032 35 4 0 43 50
R C LC o C
W   = 27wt%
wt% Ni
R S
66
 Development of microstructure
(equilibrium cooling)

 With continuous cooling, both composition and relative amounts of

each of the phases will change.
 The composition of the liquid and solid solution () phases will
follow the liquidus and solidus lines.
 The fraction of the solid phase will increase with continued cooling.

 The overall alloy composition remains unchanged.

67
 Phase diagram: Cu-Ni system.
T(°C) L (liquid) L: 35wt%Ni

• System is: 130 0 A + 

L: 35wt%Ni L
--binary : 46wt%Ni
i.e., 2 components: 35 B
46
32 C 43
Cu and Ni.
--isomorphous 24 D36 L: 32wt%Ni
i.e., complete
120 0 +  : 43wt%Ni
solubility of one
L E
component in L: 24wt%Ni
another; a phase : 36wt%Ni

field extends from
0 to 100wt% Ni. (solid)
• Consider
110 0
Co = 35wt%Ni. 20 30 35 40 50
Co wt% Ni
 Mechanical Properties: Cu-Ni System

• Effect of solid solution strengthening on:

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

60
%EL for pure Cu

Elongation (%EL)
Tensile Strength (MPa)

4 00 50 %EL for
TS for pure Ni
pure Ni 40
3 00
TS for pure Cu 30
200 20
0 20 40 6 0 8 0 10 0 0 20 40 60 8 0 10 0
Cu Ni Cu Ni
Composition, wt%Ni Composition, wt%Ni

--Peak as a function of Co --Min. as a function of Co

69
 Binary eutectic systems

 Three single-phase regions exist.

 Limited solubility of solid phases below certain temperature.

 Solvus line separates a region of one solid-phase from region of two

solid-phases (vs. solidus).

 Eutectic point is an invariant point (fixed).

 Eutectic (easy melt) reaction:

L(CE)  (CE) + (CE)

70
 Binary eutectic systems (Cont.)

 Upon cooling, eutectic reaction is similar to solidification of pure

components (i.e., reaction proceeds to completion at a constant
temperature). However, products of eutectic reaction are two phases
while products for pure component is one phase.
 Low-melting-temperature alloys are prepared having near-eutectic
compositions.

71
 T(°C)
Ex.: Cu-Ag system 120 0 Cu-Ag
• 3 single phase regions system
L (liquid)
(L, ) 10 00
• Limited solubility:  L +  779°C L+
T 8 00
: mostly Cu E 8.0 71 .9 91.2
: mostly Ni 6 00
• TE : No liquid below T E 
• CE : Min. melting T 4 00

composition 2 00
0 20 40 6 0 CE 8 0 10 0
C o , wt% Ag

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• For a 40wt%Sn-60wt%Pb alloy at 150C, find...
--the phases present:
a+b Pb-Sn system
--the compositions of T(°C)
the phases:
3 00
L (liquid)

2 00  L +  183 °C L+ 
18.3 61.9 97.8
150
1 00 

0 20 40 60 80 10 0
Co
C o , wt% Sn

73
• For a 40wt%Sn-60wt%Pb alloy at 150C, find...
--the phases present: a + b
--the compositions of Pb-Sn system
the phases: T(°C)
Ca = 11wt%Sn
3 00
Cb = 99wt%Sn L (liquid)
--the relative amounts
of each phase: 2 00  L +  183 °C L+ 
59 18.3 61.9 97.8
W  67 wt % 150
88 R S
1 00
29 
W  33 wt %
88
0 11 20 40 60 80 9910 0
Co
C o , wt% Sn

74
 Binary eutectic systems (Cont.)

 Eutectic microstructure: alternating layers (lamellae) of the two solid

phases (atomic diffusion only occur over relatively short distances).

 Hypo and hyper-eutectic systems.

75
 Microstructure in eutectic systems

T(°C) L: C o wt%Sn
4 00
• Co < 2wt%Sn L

• Result: 3 00 L
--polycrystal of a grains.
L+

2 00
TE (Pb-Sn
: C o wt%Sn
System)

1 00
+

0 10 20 30
Co Co, wt% Sn
2
(room T solubility limit)

76
 Microstructure in eutectic systems (Cont.)

T(°C) L: C o wt%Sn
4 00
• 2wt%Sn < Co < 18.3wt%Sn L
L
• Result: 3 00 
--a polycrystal with fine L+
b crystals. : C o wt%Sn

2 00
TE


1 00
+ Pb-Sn
system
0 10 20 30
2 C o C o , wt% Sn
(sol. limit at T room ) 18.3
(sol. limit at T E )
77
 • Co = C E
• Result: Eutectic microstructure
--alternating layers of a and b crystals. Micrograph of Pb-Sn
T(°C)
eutectic
L: C o wt%Sn
3 00
microstructure
L
Pb-Sn
system L+
2 00
TE  183°C L+ 

1 00 + 160 m
: 97.8wt%Sn
: 18.3wt%Sn
0
0 20 40 60 80 100
18.3 CE 97.8
61.9 C o , wt% Sn
78
 Microstructure in eutectic systems (Cont.)

• 18.3wt%Sn < Co < 61.9wt%Sn

• Result: a crystals and a eutectic microstructure
• Just above T E:
T(°C) L: C o wt%Sn  L
C  = 18.3wt%Sn
L
3 00 L  C L = 61.9wt%Sn
Pb-Sn
L+ W = S =50wt%
system R+S
2 00
TE  R S L+  WL = (1- W) =50wt%
R S
• Just below T E :
1 00
+ C  = 18.3wt%Sn
primary 
eutectic  C  = 97.8wt%Sn
0
0 20 40 60 80 100
eutectic 
W = S =73wt%
18.3 Co 61.9 97.8 R+S
Adapted from Fig. 9.14,
C o , wt% Sn W = 27wt%
Callister 6e.
79
 Hypoeutectic and hypereutectic
T(°C)
3 00 L

L+
2 00  L+ (Pb-Sn
TE 
 +  System)
1 00

Co Co
hypoeutectic hypereutectic
0 C o , wt% Sn
0 20 40 60 80 100
18.3 eutectic 97.8
61.9
hypoeutectic: C o =50wt%Sn hypereutectic: (illustration only)

eutectic: C o =61.9wt%Sn
 
 
   
 
 
175 m 160 m
eutectic micro-constituent
 Peritectic and eutectoid reactions

 Eutectic:
 One liquid phase  Solid phase(1)+Solid phase(2)

 Eutectoid (eutectic-like) reaction:

 One solid phase  two solid phases
 Peritectic reaction:
 Solid phase + Liquid phase  One solid phases
 All the above reactions involve three phases at equilibrium.

81
 Iron-Carbon system

 Ferrite ( iron) has BCC structure.

 Austenite ( iron) has FCC structure.

 Cementite is an intermediate compound.

 Carbon is an interstitial impurity in the iron-carbon system.

82
83
84
 Eutectic
eutectoid
Pearlite and
Cementine

Austenite

Ferrite
Pearlite and
Carbide
Pearlite

Steel Cast iron

• 2 important T(°C)
1600
points 
-Eutectic (A): 1400 L
L    Fe 3 C +L
 A
1200 1148°C L+Fe 3 C
-Eutectoid (B): austenite)
R S

Fe 3 C (cementite)
    Fe 3 C 1000  
  +Fe 3 C
+
800 B
 727°C = T eutectoid

R S
6 00
+Fe 3 C
4 00
0 1 2 3 4 5 6 6.7
(Fe) 0.77 4.30 C o , wt% C
120 m
Result: Pearlite = Fe 3 C (cementite-hard)
C eutectoid

alternating layers of
 and Fe 3 C phases. (ferrite-soft)

86
 Definition of structures

Various phases that appear on the Iron-Carbon equilibrium phase

diagram are as under:
•Austenite
•Ferrite
•Pearlite
•Cementite
•Martensite*
•Ledeburite
 Definition of structures

 Ferrite is known as α solid solution.

 It is an interstitial solid solution of a small amount of carbon dissolved in α (BCC)
iron.
 stable form of iron below 912 deg.C
 The maximum solubility is 0.025 % C at 723C and it dissolves only 0.008 % C at
room temperature.
 It is the softest structure that appears on the diagram.
Ferrite
 Average properties are:
 Tensile strength = 275 MPa;
 Elongation = 40 % in 2 in;
 Hardness > Rockwell C 0 or
> Rockwell B 90
 Pearlite is the eutectoid mixture
containing 0.80 % C and is formed at
723°C on very slow cooling.
 It is a very fine platelike or lamellar
mixture of ferrite and cementite.
 The white ferritic background or matrix
contains thin plates of cementite (dark).
Pearlite
 Average properties are:
 Tensile strength =827 MPa;
 Elongation = 20 % in 2 in.;
 Hardness = Rockwell C 20, Rock­well B 95-100, or
BHN 250-300.
 Austenite is an interstitial solid solution of Carbon dissolved in 
(F.C.C.) iron.
 Maximum solubility is 2.0 % C at 1130°C.
 High formability, most of heat treatments begin with this single phase.
 It is normally not stable at room temperature. But, under certain
conditions it is possible to obtain austenite at room temperature.
Austenite
 Average properties are:
 Tensile strength = 1034 MPa;
 Elongation = 10 percent in 2 in.;
 Hardness = Rockwell C 40,
approx; and
 toughness = high
 Cementite or iron carbide, is very hard, brittle intermetallic
compound of iron & carbon, as Fe3C, contains 6.67 % C.
 It is the hardest structure that appears on the diagram, exact melting
point unknown.
 Its crystal structure is orthorhombic.
 It is has
 low tensile strength (approx. 5,000 psi), but
 high compressive strength.
 Ledeburite is the eutectic mixture of austenite and cementite.
 It contains 4.3 percent C and is formed at 1130°C.
 Martensite - a super-saturated solid solution of carbon in ferrite.
 It is formed when steel is cooled so rapidly that the change from
austenite to pearlite is suppressed.
 The interstitial carbon atoms distort the BCC ferrite into a BC-tetragonal
structure (BCT).; responsible for the hardness of quenched steel
 Various Features of Fe-C diagram
Phases present
L
 ferrite
Reactions
 BCC structure
BCC structure Ferromagnetic
Peritectic L +  =  Paramagnetic Fairly ductile

Eutectic L = + Fe3C  austenite Fe3C cementite

FCC structure Orthorhombic
Eutectoid  =  + Fe3C Non-magnetic Hard
ductile brittle

Max. solubility of C in ferrite=0.022%

Max. solubility of C in austenite=2.11%
 Three Phase Reactions

 Peritectic, at 1490 deg.C, with low wt% C alloys (almost no

engineering importance).

 Eutectic, at 1130 deg.C, with 4.3wt% C, alloys called cast irons.

 Eutectoid, at 723 deg.C with eutectoid composition of 0.8wt% C,

two-phase mixture (ferrite & cementite). They are steels.

 Hypo Eutectoid steel

T(°C)
1600

1400 L
(Fe-C
   +L System)
  1200 1148°C L+Fe 3 C
austenite)

Fe 3 C (cementite)
  1000
  +Fe 3 C
 r s
  800 727°C
  R S
w  =s /(r +s ) 6 00 +Fe 3 C
w  =(1-w )
4 00
0 Co 1 2 3 4 5 6 6.7

0.77

 pearlite C o , wt% C
 w pearlite = w 
w  =S/(R+S) 100 m Hypo eutectoid
w Fe3C =(1-w ) steel

99
 Hypereutectoid steel

T(°C)
1600

1400 L
(Fe-C
   +L System)
  1200 1148°C L+Fe 3 C
austenite)

Fe 3 C (cementite)
  1000
  +Fe 3 C
Fe 3 C
  800 r s
   R S
w Fe3C =r/(r +s )6 00 +Fe 3 C
w  =(1- w Fe3C )
4 00
0 1 Co 2 3 4 5 6 6.7
0.77

pearlite C o , wt% C
w pearlite = w 
w  =S/(R+S) 6 0m Hypereutectoid
w Fe3C =(1-w ) steel

Mat. Sc. & Metallurgy by IGS 100

101
 Summary

 Solidification caused by homogeneous nucleation occurs suddenly, and only

produces a few grains.
 In heterogeneous nucleation, solidification occurs on many “seeds”, so the
grains are smaller, and more uniform.
 A solid solution may form when impurity atoms are added to a solid, in which
case the original crystal structure is retained and no new phases are formed.
 Forsubstitutionalsolidsolutions,impurityatomssubstituteforhostatoms,andappre
ciable solubility is possible only when atomic diameters and electronegativities
for both atom types are similar, when both elements have the same crystal
structure, and when the impurity atoms have a valence that is the same as or
less than the host material.
 Interstitial solid solutions form for relatively small impurity atoms that occupy
interstitial sites among the host atoms.

102
 Summary

• Phase diagrams are useful tools to determine:

--the number and types of phases,
--the wt% of each phase,
--and the composition of each phase
for a given T and composition of the system.
• Alloying to produce a solid solution usually
--increases the tensile strength (TS)
--decreases the ductility.
• Binary eutectics and binary eutectoids allow for a range of
microstructures.

103
More on Phase diagrams –Cambridge University

http://www.doitpoms.ac.uk/miclib/pds.swf?targetFrame=Al-Si

104
The taller the tree...the deeper the roots..