UMA.S.N. Assistant Professor Department of Metallurgy and Material Science College of Engineering, Pune. UMA.S.

N/MST/COEP/2014

Over view of the lecture

Cooling curve of pure metal
Concept of phase, phase rule Unary diagram of pure metal Free energy concept

Cooling curve of iron

Allotropy, free energy basis Free energy concept

Volume changes
Effect of pressure on allotropy

UMA.S.N/MST/COEP/2014

Solids

Pure metal

Alloy

UMA.S.N/MST/COEP/2014

Cooling curve of pure metal

UMA.S.N/MST/COEP/2014

UMA.S.N/MST/COEP/2014

System
Component independent constituent/chemical species

that constitutes an alloy (Eg: Fe and C in plain carbon steels) System Unary System single component (Eg: Pure metal, water) Binary System two components (Eg: water+oil, Cu-Ni, Fe-Fe3C) Ternary System Heterogeneous and homogeneous systems Systems with one phase are homogeneous Systems with more than one phase are heterogeneous
UMA.S.N/MST/COEP/2014

Phase
Phase - Chemically homogenous, Physically

(microscopically) Distinct State matter which is uniform throughout not only in chemical composition but also in physical state J. Willard Gibbs Gaseous, Liquid, Solid Phases (Single Component System) Eg: Water system ice, water, vapor. L, L1+L2, S1, S2, S, L+S, S1+S2 etc Phases (Binary System)
UMA.S.N/MST/COEP/2014

Phase diagram of a typical pure metal (Unary diagram)

UMA.S.N/MST/COEP/2014

Phase diagram/ constitutional diagram

The relationship between different phases as a function of

T,P and composition are depicted in the form of maps Phase diagram - type of chart used to show conditions at which thermodynamically distinct phases can occur at equilibrium They correspond to the state of minimum free energy of the system. So also called as Equilibrium diagrams

UMA.S.N/MST/COEP/2014

Phase rule
P+F = C+2

C number of components P number of phases present at equilibrium F degrees of freedom - number of these variables that can be changed independently without altering the number of phases that coexist at equilibrium.
When 3 phases coexist invariant point F=0. Variables = external (T and P) + internal (composition) Composition variable = no.components -1
UMA.S.N/MST/COEP/2014

Iron
M.P 1539 C B.P - 2862 C

Density - 7.874 gcm3

Atomic number -26 Atomic weight -56

world steel industry produced 1.5 billion tonnes of steel 2012 world steel association figures.

UMA.S.N/MST/COEP/2014

Cooling curve of Iron

v A4

A3 A2 curie temperature

UMA.S.N/MST/COEP/2014

Free energy diagram

iron (FCC) iron (BCC) Free energy

Liquid iron

Temperature

L
UMA.S.N/MST/COEP/2014

Volume changes

UMA.S.N/MST/COEP/2014

BCC
Effective no.of atoms = 2
No.of corner atoms no.ofbodycenteredatoms 8

Coordination number/ Ligancy = 8 Nearest no.of atoms

Volume of the atoms Packing efficiency = Volume of the unit cell = 0.68

4r Lattice parameter of BCC = 3

UMA.S.N/MST/COEP/2014

The body-centered cubic (bcc) crystal structure: (a) hard-ball model; (b) unit cell; and (c) single crystal with many unit cells
UMA.S.N/MST/COEP/2014

FCC
Effective no.of atoms = 4
Coordination number/ Ligancy = 12 Packing efficiency = 0.74 4r Lattice parameter of BCC =

No.of corner atoms No.of face centered atoms 8 2

2
Assignment: calculate packing efficiency of BCC and FCC iron.
UMA.S.N/MST/COEP/2014

The face-centered cubic (fcc) crystal structure: (a) Hardball model; (b) unit cell; and (c) single crystal with many unit cells (Effective no.of atoms, coordination number, packing efficiency) UMA.S.N/MST/COEP/2014

UMA.S.N/MST/COEP/2014

UMA.S.N/MST/COEP/2014

Effective number of atoms per unit cell

Coordination number / Ligancy

Atomic packing factor

SC BCC FCC

1 2 4

6 8 12

0.52 0.68 0.74

UMA.S.N/MST/COEP/2014

Volume change graph

iron (BCC)

iron (FCC) Volume per atom

1.6% volume change

iron (BCC)

Temperature, C

UMA.S.N/MST/COEP/2014

Properties of alpha, gamma, delta iron

Property
Atomic radius Lattice parameter Atomic packing factor No.of atoms per unit cell Coordination number Density

Alpha iron
1.241 A 2.863 A 0.68 2 8 7.87 g/cm3 @20C
UMA.S.N/MST/COEP/2014

Gamma iron
1.270 3.591 0.74 4 12 8.14

Delta iron
1.241 0.68 2 8 -

Effect of pressure Allotropy of iron

UMA.S.N/MST/COEP/2014