Rules

in
Physical Metallurgy
Dr. Prabhash Jain
Deptt. of Mechanical Engineering
University Institute of Technology
Barkatullah University, Bhopal
 Hume – Rothery’s Rules
Formed a number of Empirical Rules that govern the choice of Alloying
Elements in the Formation of Substitutional Solid Solutions by certain
factors and these are:
(i) Relative Size Factor
(ii) Chemical Affinity Factor
(iii) Relative Valency Factor
(iv) Lattice Type Factor i.e. Crystal Structure Factor
(i) Relative Size Factor:
➢ Atom size of Two metals should have within 15% of each other.
➢ With more than it results in Limited Solid Solubility i.e. only Fraction of
One Percent.
➢ An Unfavourable Relative Size Factor alone is Sufficient to Limited Solid
Solubility to a Low Value.
➢ With Favourable Relative Size Factor, other Three Factors should be
Considered in deciding the Probable Degree of Solid Solution.
 Examples of Relative Size Factor
System Element Crystal Atomic Valency Electro-
Structure Radius (Å) negativity

Cu - Zn Cu FCC 1.28 1 1.9

Zn HCP 1.39 2 1.6

Cu – Al Cu FCC 1.28 1 1.9

Al FCC 1.43 3 1.5

Ni – Cu Ni FCC 1.25 2 1.8

Cu FCC 1.28 1 1.9

Au – Ag Au FCC 1.44 1 2.4

Ag FCC 1.44 1 1.9

(iv) Lattice Type Factor i.e. Crystal Structure Factor:

➢ Metals have Similar type of Lattice Structure can form a

Complete Series of Solid Solutions.
➢ i.e. Two or more metals should have Similar Crystal
Structures such as FCC & FCC or BCC & BCC.
➢ For Complete Solid Solubility, the Size Factor must be Less
than 8%.
Ex. Tungsten Alloyed Steel: Fe & W has BCC structure
Platinum – Silver Alloy: Both have FCC structure
Cu – Ni (Binary System) : Both have FCC structure
Pt – Ag – Au (Ternary System): All have FCC structure
 GIBB’S PHASE RULE
This rule established the relationship between the Number of
Phases (P), the Number of Component (C) and the Number of
Degree of Freedom (F). The expression as:
P + F = C + n ………………….(1)
Where, P = Number of Phases i.e. Physically distinct & mechanically separable
C = the Number of Component
= Number of chemical compounds – Number of chemical and or
physical (material or charge balance) relations existing with them
F = the Number of Degree of Freedom or the number of
Intensive Parameters that must be specified in order to completely
determine the system
= Minimum number of independent variables that must be fixed in
order to understand the system fully.
n = Number of Non-Compositional Variables like Pressure, Temperature
“The values of P & F depend on the condition”
✓ Since the Non-Composition Variable includes Two External Parameters
“Temperature and Pressure” hence Equation(1) can be written as
P + F = C + 2………………….(2)
✓ In Metallurgical or Chemical system where Pressure is regarded as Fixed at
One Atmosphere or may be neglected then equation becomes
P+F=C+1
F = C + 1 - P………………….(3)
✓ Since Degree of Freedom (F) can not be Less than “Zero” therefore
C+1–P≥0
P≥C+1
i.e. Number of Phases(P) in the System can not be Exceed the
Number of Component Plus One
i.e. therefore Not more than Three Phases in the Binary System and
Not more than Four Phases in the Ternary System etc.
✓ When Maximum Possible Number of Phases (P) in the Equilibrium, the
Degree of Freedom Equals to Zero (F=0) then System is called
“Non- Variant Equilibrium”
It may Exist only under Entirely Definite Conditions i.e. at a Constant Temperature & a
Definite Composition of all Phases involved
 Examples
➢ Homogenous Chemical Equilibrium
N2(g) + 3H2(g) 2 NH3(g)
➢ Heterogonous Chemical Equilibrium
CaCO3(s) CaO(s) + CO2(g)
➢ Heterogonous Physical Equilibrium
Solid Liquid (Melting)
Liquid Vapour (Vaporization)
Solid Vapour (Sublimation)
(i) WATER SYTEM: ice water vapor
P = 1, 2 or 3 ; C = 1; F=?
(ii) SYSTEM OF (PCl5 + PCl3 + Cl2 )
PCl5 PCl3 + Cl2; P= 1; C = 3 – 1 = 2; F=?
(iii) Pb & Ag System: C= 2; P = 1, 2 or 3; F=2,1,0
There is no (chemical or physical) relation between Pb & Ag
(% Pb = 100 - % Ag is only a mathematical relation)
 Lever Rule
❖ It is the Method used to find out the Exact Amount of a Particular Phase
existing in a Binary System for a Alloy at any Temperature & Composition
under consideration.
OR
❖ The relative amounts of two phases that are in equilibrium can be
Calculated using the Lever Rule or Law, if the overall composition and the
compositions of each phase are known.
OR
❖ It is used to Determine the Amount of Phases Co-existing at Particular
Temperature & alloy composition.
 Lever Rule
Let
G – Melting Point of Metal ‘A’
H – Melting Point of Metal ‘B’
FS – Fraction of Material in Solid Phase
FL – Fraction of Material in Liquid Phase
➢ Consider an Alloy of Metal ‘A’ & ‘B’
➢ Let ‘CO’ be the Composition of Alloy
➢ ‘TA’ be the Temperature at which
Phase content is to be Found out.
➢ Curve ‘GOH’ marks Transformation
from Liquid Phase to Intermediate
Liquid + Solid Phase on Cooling
➢ Similarly Curve ‘GPH’ marks
Transformation from Intermediate
Liquid + Solid Phase to Solid Phase
on further Cooling
➢ At Temperature ‘TA’ corresponding to
point ‘M’ there are Two Phases of
Compositions ‘CL’ and ‘CS’
Lever Rule
Lever Rule
 Lever Rule: A Proof
Sum of weight fractions: F + F =1
L S
Conservation of mass (Ni): C =F C +F C
o L L S S
Combine above equations:

• A geometric interpretation:
moment equilibrium:
WLR = WS

1− W
solving gives Lever Rule
9
 Interpretation of Phase Diagram
Prediction of Number of
Phases: Consider an Alloy
of 50% Cu and 50% Ni
✓At Temp. T1 corresponding
to point ‘L’ there is One
Phase i.e. Solid
✓At Temp. T2 corresponding
to point ‘M’ there are Two
Phases i.e. Solid & Liquid
and
✓At T3 corresponding to
point ‘N’ there is One Phase
i.e. Liquid
✓Similarly Phases could be
Predicted for Different Alloys
at Different Temperatures
 Interpretation of Phase Diagram
Prediction of Chemical Composition of
Phases:
➢At Points ‘L’ and ‘N’ there is only One Phase
present and so Chemical Composition of
Phase must be same as the Composition of
an Alloy.
➢At Point ‘M’ there are Two Phases present
i.e. Liquid & Solid
➢At Temp. T2 for 50% Cu & 50% Ni and to
Determine the Chemical Composition of
Liquid & Solid, for that:
➢Draw a Horizontal Line through ‘M’ cutting
Solidus & Liquidus Line at ‘O’ and ‘P’
respectively.
➢Then Draw Vertical Lines through ‘O’ & ‘P’
to meet X-axis and Get the Chemical
Composition
Ex.
(i) At T2 Alloy of 50% Cu & 50% Ni will have Two
Phases i.e. Liquid & Solid
(ii) Single Phase; Solid of Alloy having 25% Cu
& 70% Ni
(iii) Single Phase; Liquid of Alloy having 65% Cu
& 35% Ni
Interpretation of Phase Diagram