Phase
Anything which is homogenous and physically distinct.
It can also be defined as anything which is physically distinct, chemically
homogeneous, and mechanically separable.
Any structure which is visible as physically distinct under microscope is called
phase.
For pure elements phase means the states of the metals:
Solid state –solid phase
Liquid state –liquid phase
Gaseous state-gaseous phase.
• Certain metals show allotropic modification and change its crystal structure
changing its phase.
• Example of metals showing allotropic transformation: iron, tin, zirconium,
titanium, tungsten
• In solid states three types of phases are possible to form: Pure Metal,
Compound and Solid Solution
Pure Metal:
Sharp melting and freezing point under equilibrium condition.
Cooling curve (Temp vs Time) of a pure metal shows a horizontal line at
its melting or freezing point.
Alloy:
It a combination of two or more elements from which at least one is metal,
the substance formed will must showing properties of metals.
Alloys are made by mixing the constituents in liquid state. Here one will be
the host metal and other is alloying elements.
Example of alloys: plain carbon steels, alloy steels etc.
Classification of alloy on basis of no of elements present:
Binary alloy system-990 system possible
Ternary alloy system-14000 system possible
Alloys can also classified as
1. Homogeneous alloy (consist of single phase)
2. Heterogeneous alloy or mixture (consists of multiple or mixture of phases)
Compound or Intermediate Alloy Phase:
Combination of two or more atoms in a definite proportion.
Combination of positive and negative valence elements.
After forming a compound the elements lose their individual identity and properties.
Some compound behaves like pure metals having a definite melting point with narrow
limits of temperature. So cooling curve for a compound is similar to that of a pure metal. It
is referred to as a congruent melting phase.
Chemical composition of intermediate alloy phase is intermediate between the two pure
metals and generally has crystal structure different from those of pure metals.
Intermetallic compounds
If two elements have high difference in electronegetivity, they tend to from a system
called intermetallic compound.
Intermetallic compounds like MgSe, PbSe, Mg2Si, Cu2S are cubic whereas NiAs,
MnSe, CuSn are hexagonal.
Solid solution:
It can be defined as a solution in solid state, which consists of two kinds of atoms
combined in one type of space lattice.
Example: Austenite , ferrite, delta iron, martensite
Solution may be solid, liquid or gaseous; Example – sugar or salt in water.
Solution may consist of two parts one is major part called solvent and minor called
solute.
On the basis of dissolution capacity or amount of solute present in solution there
possible condition of solution are there :
1- Unsaturated
2- Saturated
3- Supersaturated.
Solubility of solute is a function of temperature with pressure constant.
Solid solution are of two types: Substitutional and Interstitial
Phase Diagram
Phase diagrams are an important tool in the armory of an materials scientist.
In the simplest sense a phase diagram demarcates regions of existence of various
phases. (Phase diagrams are maps)
Phase diagrams are also referred to as “equilibrium diagrams” or “constitutional
diagrams”. This usage requires special attention: through 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.
Phase diagrams involving time 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.
Some Important definitions:
Phase:
A physically homogeneous and distinct portion of a material system (e.g. gas, crystal,
amorphous etc.)
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.
Components of a system:
Independent chemical species which comprise the system. These could be Elements,
Ions, and Compounds.
Example: Au-Cu system : Components →Au, Cu (elements)
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.
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.
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
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=CP+2 F – Degrees of Freedom
or C – Number of Components
The phase P – Number of Phases
rule
FC+P=2
The Phase rule is best understood by considering examples from actual phase diagrams as
shown in some of the coming slides
A way of understanding the Gibbs Phase Rule:
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
components added and P phases to produce given
&T the conditions
Variation of the number of degrees of freedom with number of components and number of phases
Degrees of Freedom
No. of phases
C – P +2
1 3
C=2 2 2
2 components 3 1
4 0
Degrees of Freedom
No. of phases
C – P +2
1 4
C=3
2 3
3 components
3 2
4 1
Cooling curve
It’s a plot between temperature and time.
Cooling curves gives us idea about the solidification start and end temperature.
Since a metal is having a sharp melting and freezing temperature we will get a
horizontal line for the cooling curve. And since alloy has a range of melting temperature
we will get a curved cooling curved. So for the pure metals beginning and end of the
solidification occurs at a constant temperature.
• Solidus: Temperature at which alloy is completely solid or temperature at which
liquefaction begins
• Liquidus: Temperature at which alloy is completely liquid or temperature at which
solidification begins
• Limits of Solid Solubility: Unlimited Solid Solubility: Solute and solvent are mutually
soluble at all concentrations, e.g., Cu-Ni. System Meets the requirements of the Hume-
Rothery Rules → Result is a “single phase alloy”
• Limited or Partial Solid Solubility: There is a limit to how much of the solute can
dissolve in the solvent before “saturation” is reached, e.g., Pb-Sn and most other systems
does not meet the requirements of the Hume-Rothery Rules → Results in a “multi-phase
alloy”
• Ex: Phase Diagram: Water-Sugar System
Question: What is the solubility limit at 20C?
Answer: 65wt% sugar.
If Comp < 65wt% sugar: syrup
If Comp > 65wt% sugar: syrup + sugar
coexist
• Solubility limit increases with T:
e.g., if T = 100C, solubility limit = 80wt% sugar.
24
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EFFECT OF T & COMPOSITION (Co)
• Each point on this phase diagram represents equilibrium
• Changing T can change # of phases: path A to B
• Changing Co can change # of phases: path B to C
B
C
A
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)
Binary phase diagrams can be 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
