MSE 2201: Lecture 1

Introduction to Phase Diagrams

Md. Al-Amin Bhuiyan Shuvo

Lecturer, Department of MSE,
KUET, Khulna

Resources
FC Campbell, PHASE DIAGRAMS: UNDERSTANDING THE BASICS, ASM International, 2012, Ch. 01
 INTRODUCTION

• The term “phase” refers to the distinct types of atomic bonding

and arrangement of elements in a material of a given chemical
composition.
• physically homogeneous state

Simplest example is three states of matter (solid, liquid, or

gas) of a pure metal.
 INTRODUCTION
• In a pure metal solid phase may also have different arrangement.

• Polymorphism
• ability of a solid to exist in more than one form

• Some pure metals also have different crystalline structure as a function of

temperature.

• Iron is an allotropic element.

Allotropy is the general term to describe solid-phase polymorphism of an element.

 INTRODUCTION

• What is alloying?

• Alloying, or mixing of two or more elements, also affects the

occurrence of phase changes.

• Temperature for complete melting (100% liquid phase) of an alloy depends on

the relative concentration of alloying elements

• Depending on the mixture of two or more elements different crystalline

phases and/or chemical compounds
 INTRODUCTION
• Phase diagrams are useful graphical representations of the phase
changes in a material.

• (1) development of new alloys for specific applications,

• (2) fabrication of these alloys into useful configurations,

• (3) design and control of heat treatment procedures for specific alloys that
will produce the required mechanical, physical, and chemical properties, and

• (4) solving problems that arise with specific alloys in their performance in
commercial applications
 INTRODUCTION
• Phase diagrams are an important tool in the armoury of an materials scientist.

• In the simplest sense a phase diagram defines regions of existence of various

phases.

• This is similar to a map which draws regions based on political, geographical,

ecological etc. criteria.
Phase diagrams are maps of materials.
Thorough understanding of phase diagrams is a must for all materials
scientists/materials engineers/metallurgists.

REMEMBER: There are many other maps that a material scientist will encounter like creep mechanism
maps, various kinds of materials selection maps etc.
 INTRODUCTION
• Phase diagrams are also referred to as “EQUILIBRIUM PHASE DIAGRAMS”.

• Broadly two kinds of phase diagrams can be differentiated → those

involving time and those which do not involve time.
• (special care must be taken in understanding the former class—those involving
time).  We will deal with this during study of Steels.

• Time-Temperature-Transformations (TTT) diagrams and Continuous-Cooling

Transformation (CCT) diagrams involve time. These diagrams are usually designed to
have an superimpose of microstructural information (including microstructural
evolution).

• W/O time type  two sub-types

• Composition as a variable (T vs %C)
• W/O Composition as a variable (T vs P)
 INTRODUCTION

So, what is
microstructure?
 UNARY SYSTEM
• Pure metals exist in three states of matter: solid, liquid, and vapour 
depending on the specific combination of temperature and pressure.

• Each of these three states is referred to as a phase; that is, the solid, liquid, and
vapour phases.

• Consider a solid block of metal in a container inside a furnace.

• Heated  Liquid
• More heating  Vapour
• Give pressure  squeezed gas  volume changes
• Remove pressure and heating  liquid
• Give pressure  no volume changes
• Remove pressure and heating  Solid
• Give pressure  no volume changes
 UNARY SYSTEM

• Therefore, during the processing of metals, the effects of pressure

and volume change can often be ignored.

• Because most metallic processes are conducted at atmospheric

pressure, the pressure in phase diagrams is normally assigned a value
of 1 atm and volume changes are ignored.

• Because the system considered so far contains only one pure metal, it
is known as a unary system.
 BINARY SYSTEM
• Now consider the addition of a second metal, for example, an alloy of
nickel and copper.

• completely miscible
• FCC
• Similar atom size

Isomorphous phase diagram

closely similar in shape

 BINARY SYSTEM
• Liquidus Curve (the upper curve)  for each possible alloy composition 
the temperature at which freezing begins during cooling or, equivalently, at
which melting is completed on heating.

• Solidus Curve (the lower curve)  the temperatures at which melting

begins on heating or at which freezing is completed on cooling.

• Above liquidus  all liquid  L

• Below solidus  all solid  α (solid phase and a solid solution)

• Between these curves  liquid and solid phases present together  L + α

BINARY SYSTEM

Melting point vs melting range

 EQUILIBRIUM
• Phase diagrams record the phase relationships under equilibrium
conditions.

• In practice, phase transformation occurs at slightly different T 

depending on the rate of heating and/or cooling.

• With rapid heating, any phase change, such as melting, occurs at a

slightly higher temperature than with slow heating.

• With rapid cooling, the phase change occurs at a lower temperature

than with slow cooling.
Transformations observed during heating are at higher temperature than the reverse transformations
observed during cooling.  Except at very slow rate of heating and/or cooling
 EQUILIBRIUM

• The equilibrium states that are represented on phase diagrams are

known as heterogeneous equilibria, because they refer to the
coexistence of different states of matter.

• Condition: For two or more phases to attain mutual equilibrium, it is

necessary that each be internally in a homogeneous state.
 EQUILIBRIUM

• An exception to the rule, that only true equilibrium states are

recorded on phase diagrams, is found in the representation of so-
called metastable equilibria.

• In carbon steels, for example, there is a solid phase, a carbide of iron (Fe3C)
called cementite, that decomposes into graphite and iron under conditions
that are favourable to the attainment of true equilibrium.

• However, the rate of decomposition of the iron carbide is extremely slow.

• Because of its reluctance to decompose, this phase is said to be metastable.

EQUILIBRIUM
 Definitions
Let us start with some basic definitions
DEFINITIONS

Components of a system

Independent chemical species which comprise the system:

These could be: Elements, Ions, Compounds
E.g.
 Au-Cu system : Components → Au, Cu (elements)
 Ice-water system : Component → H2O (compound)
 Al2O3 – Cr2O3 system : Components → Al2O3, Cr2O3 Note that
components need not
be only elements

This is important to note that components need not be just elements!!

 Definitions
Phase Physically distinct, chemically homogenous and mechanically separable region of a
system (e.g. gas, crystal, amorphous...).

 Gases
Gaseous state always a single phase
→ mixed at atomic or molecular level Three immiscible liquids
 Liquids
► Liquid solution is a single phase
→ e.g. NaCl in H2O
► Liquid mixture consists of two or more phases
→ e.g. Oil in water (no mixing at the atomic/molecular 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
 For the same crystal structure different compositions represent different phases.
E.g. in Au-Cu alloy 70%Au-30%Cu & 30%Au-70%Cu are different phases
 Definitions

What kinds of Phases exist? Textbook

 We have already seen the ‘official’ definition of a phase:

Physically distinct, chemically homogenous and mechanically separable region of a
system.

 However, the term phase is used in diverse contexts and we list below some of these.

 Based on state  Gas, Liquid, Solid

 Based on atomic order  Amorphous, Quasicrystalline, Crystalline
 Based on Band structure  Insulating, Semi-conducting, Semi-metallic, Metallic
 Based on Property  Paraelectric, Ferromagnetic, Superconducting, …..
 Based on Stability  Stable, Metastable, (also- Neutral, unstable)
 Also sometimes- Based on Size/geometry of an entity  Nanocrystalline, mesoporous, layered, …
Definitions
 Definitions
Phase Transformation
Phase Transformation is the change of one phase into another.
E.g.: ► Water → Ice
► - Fe (BCC) → - Fe (FCC)
 - Fe (FCC) → - Fe (ferrite) + Cementite (this involves change in composition)
► Ferromagnetic phase → Paramagnetic phase (based on a property)

Grain

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

a grain boundary

Microstructure An alternate definition based on magnification

 (Phases + defects) and their distributions

Structures requiring magnifications in the region of 100 to 1000 times

OR
The distribution of phases and defects in a material
 Definitions
Phase diagram
Map demarcating regions of stability of various phases. Or Map that gives relationship
between phases in equilibrium in a system as a function of T, P and composition (the restricted
form of the definition sometime considered in materials textbooks)

Variables / Axis of phase diagrams

 The axes can be:

◾Thermodynamic (T, P, V),
Other possibilities include magnetic field intensity (H), electric field (E) etc.
◾Kinetic (t) or
◾Composition variables (C, %x) (composition is usually measure in weight%, atom% or mole fraction)
 In single component systems (unary systems) the usual variables are T & P
 In phase diagrams used in materials science the usual variables are: T & %x
 In the study of phase transformation kinetics Time Temperature Transformation
(TTT) diagrams or Continuous Cooling Transformation (CCT) diagrams are also
used where the axis are T & t
 Definitions
Important points about phase diagrams

 Phase diagrams are also called Equilibrium Phase Diagrams.

 Though not explicitly stated the word ‘Equilibrium’ in this context usually means
Microstructural level equilibrium and NOT Global Equilibrium.
 Microstructural level equilibrium implies that microstructures are ‘allowed to
exist’ and the system is not in the global energy minimum state.
 This statement also implies that:

 Micro-constituents* can be included in phase diagrams

Certain phases (like cementite in the Fe-C system) maybe included in phase
diagrams, which are not strictly equilibrium phases (cementite will decompose to
graphite and ferrite given sufficient thermal activation and time)
Various defects are ‘tolerated’ in the product obtained. These include defects like
dislocations, excess vacancies, internal interfaces (interphase boundaries, grain
boundaries) etc.

* will be defined later

 THE 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: A general definition

 In response to a stimulus the ways in which the system can respond corresponds to the
degrees of freedom of the system

For a system in equilibrium F=CP+2 F – Degrees of Freedom

or C – Number of Components
P – Number of Phases
The phase rule FC+P=2

The Phase rule is best understood by considering examples from actual phase diagrams as
shown in some of the coming slides
 THE GIBBS PHASE RULE
Variables in a Phase Diagram
 C – No. of Components
 P – No. of Phases
 Variables in the system =  F – No. of degrees of Freedom
Composition variables + Thermodynamic variables

 Composition of a phase specified by (C – 1) variables

(e.g. If the composition is expressed in percentages then the total is 100%  there is one equation
connecting the composition variables and we need to specify only (C1) composition variables)
 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)

 Thermodynamic variables = P + T (usually considered) = 2

(NOTE: at constant Pressure (e.g. atmospheric pressure) the thermodynamic variable becomes 1)

 Total no. of variables in the system = P(C – 1) + 2

F < no. of variables, that is,  F < P(C – 1) + 2

 THE GIBBS PHASE RULE
 For a system in equilibrium the chemical potential of each species is same in all
the phases.
 If , , ,… are phases, then: A() = A() = A()….
Suppose there are 2 phases ( &  phases) and 3 components (A,B,C) in each phase.
Then: A() = A(), B() = B(), C() = C()  i.e., there are 3 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 = no. of variables. F=C
P + 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, ferromagnetic iron phase etc.)
 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)
 THE GIBBS PHASE RULE

A way of understanding the Gibbs Phase Rule: F=CP+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 (DoF)= What you can control  What the system controls

Can control the no. of System decided how many

components added and P phases to produce given the
and T conditions
THE GIBBS PHASE RULE
 THE GIBBS PHASE RULE
Variation of the number of degrees of freedom with number of components and number of phases
Phase rule with pressure
fixed (at say 1 atm)

No. of Total variables Degrees of Freedom Degrees of Freedom

phases
P(C – 1) +2 C – P +2 C – P +1
P
Bivariant
1 3 3 2
C=2 Univariant
2 components 2 4 2 1 3 phase co-
existence is an
3 5 1 0 invariant point

4 6 0 Not possible

No. of Total variables Degrees of Freedom Degrees of Freedom

phases P(C – 1) +2 C – P +2 C – P +1

1 4 4 3

C=3 2 6 3 2
3 components 3 8 2 1

4 10 1 0
SINGLE COMPONENT PHASE DIAGRAMS(UNARY)
 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 diagrams (in terms of the axis and phases) , we
shall only consider a T-P unary phase diagram.
 Let us consider the Fe unary phase diagram as an illustrative example.
 Apart from the liquid and gaseous phases many solid phases are possible based on crystal structure. (Diagram
on next page).

 Note that the units of x-axis are in GPa (i.e. high pressures are needed in the solid state and liquid state to
see any changes to stability regions of the phases).
 The Gibbs phase rule here is: F = C – P + 2. (2 is for T & P).
 Note that how the phase fields of the open structure (BCC- one in the low T regime () and one in the high
T regime ()) diminish at higher pressures. In fact - phase field completely vanishes at high pressures.
 The variables in the phase diagram are: T & P (no composition variables here!).
 Along the 2 phase co-existence lines the DOF (F) is 1 → i.e. we can chose either T or P and the other will be
automatically fixed.
 The 3 phase co-existence points are invariant points with F = 0. (Invariant point implies they are fixed for a
given system).
SINGLE COMPONENT PHASE DIAGRAMS(UNARY)
SINGLE COMPONENT PHASE DIAGRAMS(UNARY)
Understanding aspects of the iron unary phase diagram

 The degrees of freedom for regions, lines and points in the figure are marked in the diagram shown
before
 The effect of P on the phase stability of various phases is discussed in the diagram below.
 It also becomes clear that when we say iron is BCC at RT, we mean at atmospheric pressure (as evident
from the diagram at higher pressures iron can become HCP)

This line slopes upward as at constant T if we increase the P

Gas the gas will liquefy as liquid has lower volume (similarly you Solid/
should draw horizontal lines to understand the effect of
1 2 Increase P and gas will
pressure on the stability of various phases- and rationalize
Liquid
liquefy on crossing phase
boundary the same).
Liquid
Temperature (ºC) →

Phase fields of non-close packed structures

 (BCC) shrink under higher pressure.

Phase fields of close packed structures expand Solid/

 (FCC) under higher pressure.
Solid
These lines slope downward as: Under
 (HCP) higher pressure the phase with higher
 (BCC) packing fraction (lower volume) is
preferred.
Usually (P = 1 atm) the high temperature phase is the
Pressure (GPa) → loose packed structure and the RT structure is close packed.
How come we find BCC phase at RT in iron?
SINGLE COMPONENT PHASE DIAGRAMS(UNARY)
 BINARY PHASE DIAGRAMS
 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.
BINARY PHASE DIAGRAMS

F=CP+1
Determine DOF

Determine DOF

So, MP does not change!

 DOF IN BINARY PHASE DIAGRAMS
 We have already seen that the reduced phase rule at 1 atm pressure is:
F = C – P + 1.
The ‘one’ on RHS above is T.

 The other two variables are:

 Composition of the liquid (CL) and composition (CS) of the solid.
Or, In a fully solid state reaction:
 Composition of one solid (CS1) and composition of the other solid (CS2).

 The compositions are defined with respect to one of the components (say B):
C L B, C S B

 The Degrees of Freedom (DOF, F) are defined with respect to these variables.
 DOF IN BINARY PHASE DIAGRAMS
C=1
P=2
F=C–P+1
F=0 Variables → T, CLB  2 C=2
P = 1 (liquid)
M.P. of A Liquid F=2

Variables →  T and Composition can both be

For pure components all
transformation temperatures (BCC T, C LB, C SB  3 varied while still being in the single

T→
to FCC, etc.) are fixed (i.e. zero ‘F’) phase region

Solid + Liquid
in the two phase region, if we fix T
(and hence exhaust our DOF), the C=2
composition of liquid and solid in P=2
equilibrium are automatically fixed (i.e. F=1
we have no choice over them).
 Alternately we can use our DOF to
chose CL → then T and CS are Solid M.P. of B
automatically fixed.
Disordered (substitutional) solid solutions

C=2
Variables → T, C SB  2
P=1
F=2

A B
%B → F=2–P For binary
F=2–P F= 3 – P
For alloys
system
For pure components at any T
 SIGNIFICANCE OF DOF
THE PHASE RULE
• Gibbs’ phase rule

• This rule says that the maximum number of phases, P, which can
coexist in a chemical system, or alloy, plus the number of degrees of
freedom, F, is equal to the sum of the components, C, of the system
plus 2:

P+F= C+2

Determine under what conditions a pure metal can exist with the gas, liquid, and solid phases all present in a
state of equilibrium.
 SIGNIFICANCE OF DOF
• Suppose that it is desired to ascertain under what conditions a
pure metal can exist with the gas, liquid, and solid phases all present in a
state of equilibrium.

• DOF (F)=0

• If it is desired to construct a phase diagram in which the coexistence of the three

phases is represented,
• it becomes apparent that the coordinates of the diagram should be temperature and
pressure
• and that the coexistence of the three phases must be indicated by a single point on this
diagram.

• If one such set of specific conditions of temperature and pressure is now found by
experiment, it will be unnecessary to look for another set, because the phase rule shows that
only one can exist.
 THEOREM OF LE CHẬTELIER
• Phase rule does not provide the shape of the lines and fields on a
phase diagram.
• Hence, we need thermodynamics.

• ① The theorem of Le Chậtelier says that

• if a system in equilibrium is subjected to a constraint by which the equilibrium
is altered,
• a reaction takes place that opposes the constraint, that is, one by which its
effect is partially annulled.

• So  T phase change  occurs by heat absorption

• Also  P  phase change  occurs by a contraction in volume
 THEOREM OF LE CHẬTELIER
Typical metal contracts on freezing.

So, what
does it
mean?

Physical Significance
of this principle Campbell Page 7
 CLAUSIUS-CLAPEYRON EQUATION
• ② Clausius-Clapeyron Equation
• Each of the curves representing two-phase equilibrium must lie at such an
angle that on passing through the point of three-phase equilibrium, each
would project into the region of the third phase.
 THE LEVER RULE
• Lever Rule says
The relative amount of a given phase is proportional to the length of the tie-
line on the opposite side of the alloy point of the tie-line.

Aα Ao Aβ
THE LEVER RULE
 THE LEVER RULE

So, to get fraction of β at Ao, we can write

And, fraction of α phase is 100-37.50%=62.50%.

Aα Ao Aβ
THE LEVER RULE
Next Class
MSE 2201: Lecture 02