JAWAHARLAL NEHRU TECHNOLOGICAL UNIVERSITY HYDERABAD

Material Science and Metallurgy

II Year B.Tech.I Sem

MODULE -IV
Ms. Sindhu B
Assistant Professor C
Dpmt of Metallurgical
Engineering
JNTUHCEH
 DEPARTMENT OF METALLURGICAL
ENGINEERING
VISION
To impart quality education in Metallurgical Engineering and
constantly pursuing excellence by upgrading knowledge,
skills and attitude useful to Industry, Academic and Society.
MISSION
1. To produce graduates having professional excellence in
Basic Sciences and Metallurgical Engineering with concern
towards society.
2. To provide a scientific environment, to help meet the desires
and needs of students and faculty for enhancing research
efforts and technological innovations.
3. To provide technical support to higher education, industry
and R&D units.
Objectives
At the end of the course, the student will be able to:
Understand and analyze the crystal structure and
classification of materials and determining
mechanical properties and their suitability for
applications.
Classify cast irons and study their applications.
Interpret the phase diagrams of materials.
Select suitable heat-treatment process to achieve
desired properties of metals and alloys.
Understand the ceramics and composite materials
and their properties.
Course outcomes:
The student an able to understand basic idea of the
different material properties and heat treatment process of
ferrous and non ferrous alloys with respect to phase
diagrams.
 UNIT –II
Contents

EQUILIBRIUM OF DIAGRAMS- Experimental methods for

construction of equilibrium diagrams
 Isomorphous alloy systems
 Equilibrium cooling and heating of alloys
 Lever rule, coring
 Eutectic systems, Miscibility gaps
 Congruent melting intermediate phases- peritectic reaction.
TRANSFORMATIONS IN THE SOLID STATE – Allotropy,
Eutectoid, Peritectoid reactions
 phase rule
 Relationship between equilibrium diagrams and properties of
alloys
 Study of important binary phase diagrams of Cu-Ni, Al-Cu, Bi-
Cd, Cu-Sn and Fe-Fe3C.
Introduction
 Phase diagrams are also referred to as “equilibrium diagrams” or
“constitutional diagrams”.The term used is “equilibrium”, in practical
terms the equilibrium is not global equilibrium but Microstructural level
equilibrium.
 Broadly two kinds of phase diagrams can be differentiated*→ those
involving time and those which do not involve time.
 In this chapter we shall deal with the phase diagrams not involving
time. This type can be further sub classified into:
 Those with composition as a variable (e.g. T vs. %Composition)
 Those without composition as a variable (e.g. P vs. T)
 Time-Temperature-Transformation (TTT) diagrams and Continuous-
Cooling- Transformation (CCT) diagrams involve time. These diagrams
will be considered in the chapter on Heat treatment.
Definitions
COMPONENTS OF A SYSTEM
 Independent chemical species which comprise the system. These could be Elements, Ions,
Compounds
Example: Au-Cu system : Components →Au, Cu (elements)
Ice-water system : Component→H2O (compound)
Al2O3-Cr2O3 system : Components→Al2O3, Cr2O3

PHASE
 A physically homogeneous and distinct portion of a material system (e.g. gas, crystal, amorphous)
 Gases : Gaseous state always a single phase → mixed at atomic or molecule level.
 Liquids: Liquid solution is a single phase → e.g. Nacl in H2O and Liquid mixtures consists of two
or more phases → e.g. Oil in water (no mixing at the atomic level)
 Solids: In general due to several compositions and crystals structures many phases are possible.
 For the same composition different crystal structures represent different phases. E.g. Fe (BCC)
and Fe (FCC) are different phases
What kinds of phases exist?

 Based on state → Gas, Liquid, Solid

 Based on atomic order → Amorphous, Quasi-crystalline, Crystalline
 Based on band structure → Insulating, Semi-conducting, Semi-metallic, Metallic
 Based on Property → Para-electric, Ferromagnetic, Superconducting
 Based on stability → Stable, Metastable, Unstable
 Also sometimes- Based on size/geometry of an entity → Nanocrystalline, mesoporous,
layered.

Phase transformation
 Phase transformation is the change of one phase into another. For example
 Water → Ice and α-Fe (BCC) → γ-Fe (FCC)

Grain

 The single crystalline part of polycrystalline metal separated by similar entities by a

grain boundary
Solute
 The component of either a liquid or solid solution that is present to a lesser or minor
extent; the component that is dissolved in the solvent.

Solvent
 The component of either a liquid or solid solution that is present to a greater or major
extent; the component that dissolves the solute.

System

 System, has two meanings. First, ‘‘system’’ may refer to a specific body of material or
object. Or, it may relate to the series of possible alloys consisting of the same
components, but without regard to alloy composition

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.
Microstructure
 (Phases + defects + residual stress) & their distributions
 Structures requiring magnifications in the region of 100 to 1000 times. (or) The
distribution of phases and defects in a material.

Phase diagram
 Map that gives relationship between phases in equilibrium in a system as a function of T,
P and composition.

Variables/Axis of phase diagrams

 The axes can be:
 Thermodynamic (T, P, V)
 Kinetic (t) or Composition variables (C, %X)
 In single component systems (unary systems) the usual variables are T & P
 In phase diagrams used in materials science the usual variable are T & %X
 In the study of phase transformation kinetics TTT diagrams or CCT diagrams are also
used where the axis are T & t
System Components

Phase diagrams and the systems they describe are often classified and named for
the number (in Latin) of components in the system:

Number of components Name of system or diagram

One Unary
Two Binary
Three Ternary
Four Quaternary
Five Quinary
Six Sixinary
Seven Septenary
Eight Octanary
Nine Nonary
Ten Decinary
 Coordinates of Phase Diagrams
 Phase diagrams are usually plotted with temperature, in degrees centigrade or
Fahrenheit, as the ordinate and the alloy composition in weight percentage as
the abscissa.
 The weight % of component weight of component A
A: WA  100
Σ Weight of all components

 The atom (or mol)% of component A

number of atoms (or mols) of component A
XA 10
Σ number of atoms (or mols) of all components
 0

 The Conversion from weight percentage to atomic percentage may be made by

the following formulas:
X Y
M
Atomic percent of A  100
Atomic percent of B  N  10
M
X  Y    M 0
N X  Y  
N

M = atomic weight of metal A & N = atomic weight of metal B

X = weight percentage of metal A & Y = weight percentage of metal B
 Experimental Methods
Thermal Analysis
A plot is made of temperature vs. time, at constant composition, the resulting cooling curve
will show a change in slope when a phase change occurs because of the evolution of heat by
the phase change. This method seems to be best for determining the initial and final
temperature of solidification. Phase changes occurring solely in the solid state generally
involve only small heat changes, and other methods give more accurate results.

Metallographic Methods
This method consists in heating samples of an alloy to different temperatures, waiting for
equilibrium to be established, and then quickly cooling to retain their high temperature
structure. The samples are then examined microscopically. This method is difficulty to apply
to metals at high temperatures because the rapidly cooled samples do not always retain their
high temperature structure, and considerable skill is then required to interpret the observed
microstructure correctly.

X-ray diffraction
Since this method measures lattice dimensions, it will indicate the appearance of a new
phase either by the change in lattice dimension or by the appearance of a new crystal
structure. This method is simple, precise, and very useful in determining the changes in
solid solubility with temperature
 Gibbs Phase Rule
 The phase rule connects the Degrees of Freedom, the number of components
in a system and the number of phases present in a system via a simple
equation.
 To understand the phase rule one must understand the variables in the system
along with the degrees of freedom.
 We start with a general definition of the phrase “degrees of freedom”.

Degrees of Freedom
The degree of freedom, F, are those externally controllable conditions of
temperature, pressure, and composition, which are independently variable and
which must be specified in order to completely define the equilibrium state of the
system. F=C–P+ F – Degrees of Freedom
For a system in 2 or C – Number of Components
equilibrium
F-C+P= P – Number of Phases
2
The degrees of freedom cannot be less than zero so that we have an upper limit to
the number of phases that can exist in equilibrium for a given system.
 Gibbs Phase Rule
Variables in a phase diagram
o C – No. of components
o P – No. of phases
o F – No. of degrees of freedom
o Variables in the system = Composition variables + Thermodynamic variables
o Composition of a phase specified by (C – 1) variables (If the composition is
expressed in
%ages then the total is 100% → there is one equation connecting the composition variables and we
need to specify only (C - 1) composition variables)
o No. of variables required to specify the composition of all phases: P(C – 1) (as
there are P phases and each phase needs the specification of (C – 1) variables)
o Thermodynamic variables = P + T (usually considered) = 2 (at constant pressure
(e.g. atmospheric pressure) the thermodynamic variable becomes 1)
o Total no. of variables in the system = P (C – 1) + 2
o F < no. of variables → F < P (C – 1) + 2
 Gibbs Phase Rule
o For a system in equilibrium the chemical potential of each species is same in all the
phases
 If α, β, γ… are phases, then: μA (α) = μA (β) = μA (γ)…..
 Suppose there are 2 phases (α and β phases) and 3 components (A, B, C) in each phase then : μA(α) =
μA(β), μB(α) = μB(β), μC(α) = μC(β) → i.e. there are three equations. For each component there are (P –
1) equations and for C components the total number of equations is C(P – 1). In the above example the
number of equations is 3(2 – 1) = 3 equations.
 F = (Total number of variables) – (number of relations between variables)
= [P(C – 1) + 2] – [C(P – 1)] = C – P + 2
 In a single phase system F = Number of F=C–P+
variables 2
 P↑ → F↓ (For a system with fixed number of components as the number
phases increases the degrees of freedom decreases.

It is worthwhile to clarify a few terms at this stage:

 Components ‘can’ go on to make a phase (of course one can have single component phases as well e.g. BCC
iron phase)
 Phases ‘can’ go on to make a microconstituent.
 Microconstituents ‘can’ go on to make a microstructure (of course phases can also directly go on to make a
microstructure)
 Gibbs Phase Rule
A way of understanding the Gibbs Phase Rule : P + F = C + 2
The degrees of freedom can be thought of as the difference between what you
(can) control and what the system controls

F = C+2 - P

Degrees of freedom = What you can control - What the system controls
Can control the no. of System decided how many phases to
components added and P&T produce given the conditions

Variation of the number of degrees of freedom with number of components and number of phases

C=2 No. of Total Variables Degrees of freedom Degrees of freedom

P(C-1)+2 C-P+2 C-P+1
Phases

1 3 3 2
2 4 2 1
3 5 1 0
4 6 0 Not possible
 Unary Phase Diagram
 Let us start with the simplest system possible: the unary system wherein there is just one
component.
 Though there are many possibilities even in unary phase diagram (in terms of the axis
and phases), we shall only consider a T-P unary phase diagram.
 Let us consider the water (H2O) unary
phase diagram
 The Gibbs phase rule here is: F=C-P+2
(2 is for T&P) (no composition
variables here)
 Along the 2 phase co-existence (at B & C
C) lines the degree of freedom (F) is 1 B
→ i.e. we can chose either T or P and the A
other will be automatically fixed.
D
 The 3 phase co-existence points (at A)
are invariant points with F=0. (Invariant
point implies they are fixed for a given
system).
 The single phase region at point D, T and
P can both be varied while still being in
the single phase region with F = 2.
 Unary Phase Diagram
160
0
δ
120
0
Temperature (ºC)
80 γ
0

40
0 α ε

0
50 100 15
Pressure / 0
kbar

The above figure represents the phase diagram for pure iron. The triple point
temperature and pressure are 490ºC and 110 kbars, respectively. α, γ and ε
refer to ferrite, austenite and ε-iron, respectively. δ is simply the higher
temperature designation of α.
 Binary Phase Diagram
 Binary implies that there are two components.
 Pressure changes often have little effect on the equilibrium of solid phases
(unless of course we apply ‘huge’ pressures).
 Hence, binary phase diagrams are usually drawn at 1 atmosphere pressure.
 The Gibbs phase rule is reduced to:
 Variables are reduced to : F = C – P + 1 (1 is for T).
 T & Composition (these are the usual variables in materials phase diagrams)

Phase rule for condensed phases F=C–P+1

For T

 In the next page we consider the possible binary phase diagrams. These have
been classified based on:
 Complete solubility in both liquid & solid states
 Complete solubility in both liquid state, but limited solubility in the solid
state
 Limited solubility in both liquid & solid states
Overview of possible Binary Phase Diagram
Liquid State Solid State

Isomorphous Solid state analogue

of isomorphous
Complete Solubility in both Isomorphous with
liquid & Solid states ordering

Isomorphous with
Phase
separation
Eutectic Eutectoid
Complete solubility in liquid
state but limited solubility
in the solid state
Peritectic Peritectoid

Monotectic Monotectoid

Limited solubility in both

Syntectic
liquid & Solid states
Metatectic
Isomorphous Phase Diagram
 Isomorphous phase diagrams form when there is complete solid and
liquid solubility.
 Complete solid solubility implies that the crystal structure of the two
components have to be same and Hume-Rothery rules to be followed.
 Examples of systems forming isomorphous systems: Cu-Ni, Ag-Au, Ge-Si,
Al2O3- Cr2O3
 Both the liquid and solid contain the components A and B.
 In binary phase diagrams between two single phase regions there will be a two
phase region → In the isomorphous diagram between the liquid and solid
state there is the (Liquid + Solid) state.
 The Liquid + Solid state is NOT a semi-solid state → it is a solid of fixed
composition and structure, in equilibrium with a liquid of fixed composition.
 In some systems (e.g. Au-Ni system) there might be phase separation in
the solid state (i.e.,the complete solid solubility criterion may not be followed)
→ these will be considered as a variation of the isomorphous system (with
complete solubility in the solid and the liquid state.
cooling curves : Isomorphous
system L
L
L
L TL S
L TL
TNi
L+S
L S L+S
Temperature (ºC)

Pure Ni
TS
S
S S
TCu
Cu-20%Ni
TS
Cu-10%Ni
Pure Cu
t
Time
(t)
 Revision : Solidification
(cooling) curves
Pure metal Alloy

L Soldificatio
L
n begins
TL
L S L+S
Tm
TS
Solidificatio S
S
n complete

Time Time
(t) (t)
 Isomorphous Phase Diagram
T and Composition can both be
varied while still being in the C=1
single phase region
P=2
C=2 F=0
P=1 Liquidus 1457ºC
(liquid) Liquid
F=2 (L)
C=2
P=2
L+
Temperature →

(L+S)
S F=
In the 1 two
Solidus region,
phase if we fix T
(and hence exhaust
1080º our DOF),
C composition of
the
and
liquid in
solid
equilibrium
Solid are automatically
fixed (i.e. we have
(S) no choice
them).Alternatively
over
C=2 we can use our
P=1 DOF to chose CL
(Solid) C % Ni Ni and T
then Cs
automatically
are
F=2 u → fixed.
T and Composition can both be
varied while still being in the
single phase region
 Tie line and Lever rule
Chemical Composition of Tie Line Rule
Phases
 To determine the actual chemical composition of the phases of an alloy, in
equilibrium at any specified temperature in a two phase region, draw a
horizontal temperature line, called a tie line, to the boundaries of the field .
These points of intersection are dropped to the base line, and the composition
is read directly.
Relative Amounts of Each Lever Rule
Phase
 To determine the relative amounts of the two phases in equilibrium at any
specified temperature in a two phase region , draw a vertical line representing
the alloy and a horizontal temperature line to the boundaries of the field.
 The vertical line will divide the horizontal line into two parts whose lengths
are inversely proportional to the amount of the phases present. This is also
known as Lever rule.
 The point where the vertical line intersects the horizontal line may be
considered as the fulcrum of a lever system.
 The relative lengths of the lever arms multiplied by the amounts of the phases
present must balance.
 Tie line and Lever rule
 We draw a horizontal line (called the Tie Line)at the temperature of interest
(say T0). Let Tie line is XY.
 Solid (crystal) of composition C 1 coexists with liquid of composition C 2
 Note that tie lines can be drawn only in the two phase coexistence regions
(fields). Though they may be extended to mark the temperature.
 To find the fractions of solid and liquid we use the lever rule.

 The portion of the horizontal line in the Arm of the lever Arm of the lever
proportional to proportional to
two phase region is akin to ‘lever’ with the Liquid Coolin the Solid
g
the fulcrum at the nominal composition
(C0)

Temperature →
 The opposite arms of the lever are Y
proportional to the fraction of the solid X
and liquid phase present (this is lever
rule)
Fulcrum of the lever

f liquid  C0  C1 f Solid  C2  C0
C2  C1 C2  C1
A C1 C0 C2 B
%
B→
Example
Tie line and Lever rule
Cu – Ni System

A
At Co = 35 wt% TA tie line
Ni L
1300
(liquid)

Temperature (ºC)
At T A : Only Liquid (L)
B
Wliquid = 100 wt%, Wsolid TB R
a
S
At T D: = 0Only Solid (S ) 1200
TD D S (solid)
W L= 0, W solid= 100 wt%
20 3 032 35 4 0 43 50
CL Co
At T B : SBoth S and L Ca
WL = 43  35
R+S  43  32 73 wt% % Ni→
Notice: as in a lever “the opposite leg” controls
with a balance (fulcrum) at the ‘base
composition’ and R+S = tie line length =
R
WS = = 27 wt% difference in composition limiting phase
R+S boundary, at the temp of interest
 The Lever Rule
 The Lever rule gives the weight % of phases
in any two phase regions.
Wt fraction of solid phase
= Xs = w0 – w1
ws – w1

Wt fraction of liquid phase

= Xl = ws – w0
ws – w1
W0 is the weight percentage of the
alloy.
Ws is the weight percentage within
the solid phase
Figure 8.5
Wl is the weight percentage in the
liquid phase
8-7
 Equilibrium Cooling

Figure: The above figure represents the very slow cooling , under equilibrium conditions, of a
particular alloy 70A-30B will now be studied to observe the phase changes that occur .
 Phase Diagram from Cooling Curves
 Series of cooling curves at different metal
composition are first constructed.
 Points of change of slope of cooling curves
(thermal arrests) are noted and phase
diagram is constructed.
The greater the number of cooling curves
the more accurate the phase diagram.

Figure 8.4
8-6
 Equilibrium Cooling
 This alloy at temperature T0 is a homogeneous single-phase liquid solution (a)
and remains so until temperature T1is reached. Since T1is on the liquidus line,
freezing or solidification now begins.
 The first nuclei of solid solution to form α1 will be very rich in the higher melting
point metal A and will be composed of 95A-5B (by tie line rule). Since the solid
solution in forming takes material very rich in A from the liquid, the liquid must
get richer in B. Just after the start of solidification, the composition of the liquid
is approximated as 69A-31B (b).
 When the lower temperature T2 is reached, the liquid composition is at L2. The
only solid solution in equilibrium with L2 and therefore the only solid solution
forming at T2 is α2. Applying tie line rule, α2 is composed of 10B. Hence, as the
temperature is decreased, not only does the liquid composition become richer in
B but also the solid solution.
 At T2 ,crystals of α2 are formed surrounding the α1 composition cores and also
separate dendrites of αz (see figure in below).
 Equilibrium Cooling
 In order for equilibrium to be established at T2, the entire solid phase must be a
composition α2. This requires diffusion of B atoms to the A-rich core not only
from the solid just formed but also from the liquid. This is possible in crystal
growth (c).
 The composition of the solid solution follows the solidus line while the
composition of liquid follows the liquidus line, and both phases are becoming
richer in B.
 At T3 (d), the solid solution will make up approximately three-fourths of all the
material present.
 Finally, the solidus line is reached at T4, and the last liquid L4, very rich in B,
solidifies primarily at the grain boundaries (e).
 However, diffusion will take place and all the solid solution will be of uniform
composition α(70A-30B), which is the overall composition of the alloy (f).
 There are only grains and grain boundaries. There is no evidence of any
difference in chemical composition inside the grains, indicating that diffusion
has made the grain homogeneous.
 Equilibrium Cooling
 The very slow cooling , Cu-Ni Phase
under
equilibrium conditions, Diagram
L (liquid) L: 35wt
of
particular alloy 65Cu - 35Ni %Ni
will now be studied.
1300 A
A – Homogeneous single L: 35 wt%
phase (Liquid) Ni a: 46 wt
% Ni 3B 35 B
46
B - ‘B’ is on the liquidus line,

Temperature (ºC)
C 43
solidification now begins. C D
24 36 L: 32 wt%
2 Ni
C – Solid surrounded by liquid
E a : 43 wt% Ni
crystals. 120 E
0
L: 24 wt%
D – ‘D’ is on the solidus line,
solidification now ends. Ni a : 36 wt
S (solid)
E – Homogeneous single phase % Ni
(Solid)
1100
2 30 35 40 50
0
Co Ni
Cu
%
Ni→
 Non Equilibrium Cooling - Coring
 In actual practice it is extremely difficult to cool under equilibrium conditions.
Since diffusion in the solid state takes place at a very slow rate, it is expected
that with ordinary cooling rates there will be some difference in the conditions
as indicated by the equilibrium diagram.
 Consider again 70A-30B
alloy, solidification starts at
T1 forming a solid solution of
composition α1 .
 At T2 the liquid is L2 and the
solid solution now forming is
of composition α2 . Since
diffusion is too slow to keep
pace with crystal growth, not
enough time will be allowed
to achieve uniformity in the
solid, and the average
composition will be between
α1 and α2, say α’2.
 Non Equilibrium Cooling - Coring
 As the temperature drops, the average composition of the solid solution will
depart still further from equilibrium conditions. It seems that the composition
of the solid solution is following a “nonequilibrium” solidus line α1 to α’5,
shown dotted lines in figure.
 The liquid, on the other hand, has essentially the composition given by the
liquidus line, since diffusion is relatively rapid in liquid. At T3 the average
solid solution will be of composition α’3 instead of α3.
 Under equilibrium cooling, solidification should be complete at T4 ; however,
since the average composition of the solid solution α’4 has not reached the
composition of the alloy, some liquid must still remain. Applying lever rule at
T4 gives α’4 = 75% and L4 = 25%.
 Therefore, solidification will continue until T5 is reached. At this temperature
the composition of the solid solution α’5 coincides with the alloy composition,
and solidification is complete. The last liquid to solidify, L5, is richer in B than
the last liquid to solidify under equilibrium conditions.
 Non Equilibrium Cooling - Coring
 The more rapidly the alloy is cooled the greater will be the composition range in
the solidified alloy. Since the rate of chemical attack varies with composition,
proper etching will reveal the dendritic structure microscopically (see below
figure). The final solid consists of a “cored” structure with a higher-melting
central portion surrounded by the lower-melting, last-to-solidify shell. The above
condition is referred to as coring or dendritic segregation.

Dendritic Structure
 To summarize, nonequilibrium cooling results in an increased temperature range
over which liquid and solid are present; Since diffusion has not kept pace with
crystal growth, there will be a difference in chemical composition from the center
to the outside of the grains. The faster the rate of cooling, the greater will be the
above effects.
 Cored vs. Equilibrium Phases
Consider Cu-Ni phase diagram case

First a to solidify has Csolid = 46 wt% Ni.

Last a to solidify has Csolid = 35 wt% Ni.

On Fast rate of cooling On Slow rate of cooling

Cored structure Equilibrium structure

First a to solidify: 46 wt% Ni Uniform Csolid

35 wt% Ni
Last a to solidify:
< 35 wt% Ni
 Homogenization
 Cored structures are most common in as-cast metals. From the earlier
discussion of the origin of a cored structure, it is apparent that the last solid
formed along the grain boundaries and in the inter-dendritic spaces is very
rich in the lower-melting- point metal.
 Depending upon the properties of the lower-melting-point metal, the grain
boundaries may act as a plane of weakness. It will also result in a serious lack
of uniformity in mechanical and physical properties and, in some cases,
increased susceptibility to intergranular corrosion because of preferential
attack by corrosive medium. Therefore, for some applications a cored
structure is objectionable.
 There are two methods for solving the problem of coring. One is to prevent its
formation by slow freezing from the liquid, but this result in large grain size
and requires a very long time. The preferred method industrially is to achieve
equalization of composition or homogenization of the cored structure by
diffusion in the solid state.
 At room temperature, for most metals, the diffusion rate is very slow; but if the
alloy is reheated to a temperature below the solidus line, diffusion will be
more rapid and homogenization will occur in a relatively short time.