Principles of Physical Metallurgy

Lecture 2+3: Equilibrium Diagrams

 Equilibrium Diagram
• Equilibrium diagrams(or Phase diagrams) are graphical
representations used to study the existence of of various phases in
the system at any temperature and composition.
• Uses of equilibrium diagram:
1. To show what phases are present at different temp. and
composition under equilibrium cooling condition
2. To indicate equilibrium solubility of one element into another.
3. To indicate temp. at which freezing and melting occurs. And temp.
range over which solidification occur.
4. To predict the microstructure of an alloy at given temp.
5. To calculate relative amount of phases present in binary system.
Terminologies
• System : System is part of universe under consideration. Or
body of matter completely cut off from its surrounding.And
is combination of phases of one or more component at
different pressure and composition.
• Equilibrium : A system is said to be in equilibrium if no
macroscopic changes takes place with time.
• Phase : It is homogeneous ,physically distinct and
mechanically separable part of the system.
• Variables :Parameters at which phase exists. ex. Temp,
pressure, concentration.
Terminologies
• Component : The element presents in the system are called
as component.
• Alloy: It is mixture of two or more elements having metallic
properties. The element present in the largest proportion is
metal and other can be metal or non metal.
• Solvent: A major element of solid solution,
• Solute : A minor element of solid solution.
Solid Solution
• Definition : Solid solution is an alloy in which the atoms of solute are
uniformly distributed in solvent and has the same structure as that
of solvent.
• Properties of solid solution:
• Thermal and electrical properties are reduced by the formation of
solid solution
• In general ,all alloying elements increase strength and hardness of
materials
• Malleability and ductility is generally decreased by the formation of
solid solution.
• Modulus of elasticity and stiffness of the solid solution is not much
affected.
Types of solid solution
• Substitutional Solid Solution: Foreign (solute) atoms occupy “normal” lattice
sites occupied by matrix (solvent) atoms, e.g. Cu-Ni;Ge-Si
• Interstitial Solid Solutions: Foreign (solute) atoms occupy interstitial sites,
e.g., Fe-C Interstitial Solid Solutions
• 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
Substitutional and interstitial solid solutions
 Hume-Rothery’s Rule 1
• Atomic Size Factor (the 15%) Rule. Extensive substitutional solid
solution occurs only if the relative difference between the atomic
diameters (radii) of the two species is less than 15%.
• If the difference > 15%, the solubility is limited. Comparing the atomic
radii of solids that form solid solutions, the empirical rule given by
Hume-Rothery is given as:
• %Difference in radius (Atomic size factor) =
{R(solvent)-R (Solute)}/R(solvent) *100
 Hume-Rothery’s Rule 2 , 3 and 4
• Hume-Rothery Rule 2:Crystal Structure Rule . For appreciable solid solubility,
the crystal structures of the two elements must be identical.
• Hume-Rothery Rule 3: Valency Rule .A metal of higher valency can dissolve
only small amount of lower valency metal while lower valency metal may have
good solubility for higher valency metal. The solute and solvent atoms should
typically have the same valence in order to achieve maximum solubility.
• Hume-Rothery Rule 4: The Electronegativity Rule . Electronegativity
difference close to 0 gives maximum solubility. The more electropositive one
element and the more electronegative the other, the greater is the likelihood
that they will form an intermetallic compound instead of a substitutional solid
solution. The solute and the solvent should lie relatively close in the
electrochemical series. Greater the chemical affinity of two metals ,the more
restricted is the solubility and greater is tendency of compound formation.
 Gibbs Phase rule
• Gibb’s Phase Rule (General): P+F =C+n
• Where P : No. of phases
F : Degree of freedom
C : No. of components
n : No. of variables( P,T)
• The degrees of freedom, F (no. of independently variable factors),
• F = C – P + 2 Number of external factors = 2 (pressure and
temperature).
• For metallurgical system pressure has no appreciable effect on phase
equilibrium and hence, F = C – P + 1
 Phase Diagrams One component system
• The simplest phase diagram is the water which is a one component
system. It is also known as pressure-temperature or P-T diagram. Two
phases exist along each of the three phase boundaries. At low
pressure (0.006 atm) and temperature (0.01 0C) all the three phases
coexist at a point called triple point.
 Binary Phase Diagrams
• Isomorphous System: When the two metals are soluble in each other
in the entire range of compositions in both liquid and solid state. This
kind of system is known as ‘Isomorphous’ system
 Eutectic System
• When two metals are completely soluble in liquid state and
completely insoluble in solid state.
• Liquid=Solid1 +Solid 2
 Partial Eutectic System
• When two metals are completely soluble in liquid state and partially
soluble in solid state.
Peritectic system
• Liquid + solid1=Solid 2