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transformations
Robin Perry
School of Physics and Astronomy,
Edinburgh
Definition of terms :
Phase, K: portion of the system with homogeneous properties and composition.
Physically distinct.
Components, C : chemical compounds that make up a system
G = E + PV TS + N
Chemical potential or partial molar free energy governs how the free energy
changes with respect to the addition/subtraction of atoms.
This is particularly important in alloy or binary systems.
(particle numbers will change)
2. Gibbs free energy, equilibrium and chemical potential, Gibbs phase rule
C, number of components
K, number of phases in equilibrium
3. Single component systems
TM T (K)
For pressure dependence:
Similar arguments apply : Vliquid > Vsolid so increasing P implies liquid to solid transition
Clausius Clapeyron Equation
more
dense
(intermediate)
more
dense
Less
dense
Less
dense
4. Binary (two component) systems : Ideal solutions
Where Hmix is the heat absorbed or evolved during mixing or heat of solution
SMIX is the entropy difference between the mixed and unmixed states
4. Binary (two component) systems : Ideal solutions
Some assumptions :
1. Free energy change is only due to entropy
2. Species A and B have the same crystal structure
(no volume change)
3. A and B mix to form substitutional solid solution
AXA = GA +RTlnXA
BXB = GB +RTlnXB
Define: HMIX= CAB where CAB is the number of A-B bonds and = AB (AA +BB)
Point of note:
GMIX always decreases on addition of solute
Free energy curves for various conditions:
Mixing if A and
B atoms bond
Mixing always
occurs at high
Temp. despite
bonding
A and B atoms
repel
Phase separation
in to 2 phases.
4. Binary (two component) systems : Activity, a of a component
A = GA + RT ln aA GA
GMIX -RTln aB
B = GB + RT ln aB
-RTln aA
It is another means of describing the state B
of the system. Low activity means that the A
atoms are reluctant to leave the solution
(which implies, for example, a low vapour 0 XB 1
pressure).
HMIX > 0
HMIX < 0
Homogeneous mixing
5. Binary phase diagrams : The Lever rule
Solid, S
A X0 B
At temperature, T and molar fraction X0, the solid and liquid phase will coexist in
equilibrium according the ratio:
nl = nl
Where n/n is ratio of liquid to solid
Solid to liquid phase diagram in a two component system : A and B are completely
miscible and ideal solutions
5. Binary phase diagrams : The Miscibility gap
HMIX > 0
G G T2
T1
solid L
a b c d
S
Common tangent
liquid
A B A B
S
2 phase: (A+B) and (B+A)
e f Compositions e and f ;
T3 e f The miscibility gap
A B
A XB B
Titanium-Vanadium revisited
(hcp)
(bcc)
For systems with phase separation ( and ) of two stable structures (e.g. fcc and bcc),
we must draw free energy curves.
G is the curve for A and B in fcc structure ( phase)
G is the curve for A and B in bcc structure ( phase)
Common tangent
If e<X0>e then minimum free energy is Ge
And two phases are present
(ratio given by the Lever rule see later)
When two phases exist in equilibrium, the activities of
the components must be equal in the two phases:
4. Binary (two component) systems : Ordered phases
(fcc)
(fcc)
Single phases Mixed phases
N.B. Always read the legend!!! (blue is not always singe phase)
An intermediate phase is a mixture that has different structure to that of either
component
Range of stability depends on structure and type of bonding (Ionic, metallic, covalent)
Intermetallic phases are intermediate phase of integer stoichiometry e.g. Ni3Al
1 phase, solid
Two phase
Single phase
Eutectic point
Phase is A with B dissolved (crystal structure A)
Phase is B with A dissolved (crystal structure B)
Example : http://www.soton.ac.uk/~pasr1/index.htm
K(Na) + KNa2
(hcp)
KNa2 + Na(K)
(bcc) (bcc)
5. Binary phase diagrams : Additional equations
So far we have assumed that every atomic site in the lattice is occupied. But this is not
always so. Vacancies can exist in the lattice.
Removing atoms: increase internal energy (broken bonds) and increases configuration
entropy (randomness).
GV=HV TSV
Where HV is the increase in enthalpy per mole of vacancies added and SV is the
change in thermal entropy on adding the vacancies (changes in vibrational frequencies
etc.).
XV is typically 10-4-10-3 at the melting point of the solid.
B. Gibbs-Duhem relationship
This relates the change in chemical potential that results from a change in alloy
composition:
5. Binary phase diagrams : Ternary phase diagrams
These are complicated.