Classification of Phase Transformations

f(x) 1 x  0 Functions and discontinuity in differentials


f ( x)   0 x  0
1 x0

x

x  0 g ( x)   (1)dt  [t ]x1  ( x  1)

1

g(x) x  0 g ( x)  1 (by definition)

0 x

x  0 g ( x)   (1)dt   (1)dt  [t ]1  [t ]0   (1  x)  ( x  1)

0 x

1 0

x
x
t2   x2  1   x2 1
x0 h ( x )  1  (t  1) dt   
 2
 t 
 1
  
 2
 x  
 2
 1 

  
 2
 x  
2
h(x)
x  0 h(0)   1 (by definition)
2
x0      1   x2   x2
0 x
 t  t2    1
0 x 2
h( x)   (t  1)dt   (t  1)dt     t     t        1     x      x  
   
2  1  2  0   2   2 
   2
1 0  2
 1

0.75

0.5

Discontinuity in 0.25
the curvature
0
-1 -0.75 -0.5 -0.25 0 0.25 0.5 0.75 1

-0.25 Discontinuity in
the slope
g(x) -0.5

Discontinuity in
-0.75
the function h(x)
f(x)
-1
 A Order of a phase transformation
Thermodynamics Ehrenfest, 1933
Based on

Classification of B
Phase Mechanism Mechanistic Buerger, 1951
Transformations
C
Kinetics le Chatelier, (Roy 1973)
 Breaking of bonds and formation of new ones
 Atom movements from parent to product by diffusional jumps
 Nearest neighbour bonds broken at the transformation front and the product structure is reconstructed by
placing the incoming atoms in correct positions → growth of product lattice

 Diffusional transformation
 Even in case chemical composition same (parent & product) + strict orientation relation
→ Still lattice correspondence not present
E.g.: Precipitation in
Al-Cu alloys
Reconstructive Diffusional → Civilian  Nucleation of product
 Growth
B Subset Replacive → e.g. ordering
Mechanistic
Buerger, 1951
Displacive Military
Cooperative motion of a large number of atoms
Homogenous distortion
E.g.: Martensitic
 Formation of nucleus of
Shuffling of lattice planes or a combination
product
 Movement of shear front
at speed of sound Static displacement wave
 Shuffle dominated

Lattice strain dominated

Magnitude of shuffle and of homogenous lattice strain

Presence of precursor mechanical instability

Structural basis

Displacive

Homogenous distortion

Shuffling of lattice planes

Static displacement wave

 Coordination between neighbours retained in the product lattice (though bond angles change)
 Atomistic coordination inherited → chemical order in parent structure is fully retained in the product
structure
 similar correspondence of crystallographic planes
 Lines → lines; planes → planes (vector, plane, unit cell correspondence)
 AFFINE TRANSFORMATION

In general, an affine transform is composed of linear transformations (rotation, scaling or shear) and a translation (or "shift").
 NOTE:
Lattice correspondence does NOT imply ORIENTATION RELATION
 as phase transformations may involve rigid body rotations
Buerger’s classification: full list

 Transformation involving first coordination

 Reconstructive (sluggish)
 Dilatational (rapid)
 Transformation involving second coordination
 Reconstructive (sluggish)
 Displacive (rapid)
 Transformations involving disorder
 Substitutional (sluggish)
 Rotational (rapid)
 Transformations involving bond type (sluggish)
 Non-quenchable Athermal → Rapid
C Subset Replacive → e.g. ordering
Kinetic
le Chatelier, (Roy 1973) Quenchable Thermal → Sluggish

* Usually Martensitic transformations are athermal- however there are instances of they being isothermal
A Thermodynamic classification Ehrenfest, 1933
Order of a phase transformation

  n1 (thermodynamic Variable)  The lowest derivative (n) which shows a

 n 1 
  (External Variable) 
discontinuity at the transition point

  n 1 (G)    n (G) 
 n 1 
0  n 
0
  (T) T TC  (T)  P

 Can be used for equilibrium transitions of single component systems

 There are cases of mixed order transformations
 In thermal transformations: usually the high-T form is of higher symmetry and
higher disorder
n=1 First Order Finite discontinuity G  H  T S
dG  VdP  SdT
  (G) 
0
  (G)  H
1
 0 
0  1
  S   (G) 
 (T) T TC  (T)  P TC   (T)    S
 P
 1 (G)  H d 2G CP
 1
  S  0 dS
G  0  (T)  P TC dT 2

dT

T
P P

 First order transitions are characterized by discontinuous changes in entropy, enthalpy &
specific volume.
 H → change in enthalpy corresponds to the evolution of Latent Heat of transformation
 The specific heat [J/K/mole] is thus infinite (i.e. at the transition heat is being put into the
system but the temperature is not changing)
Schematics
G  0

 1 (G)  H
 1
  S  0
 (T)  P TC

d 2G dS CP
   
dT 2 P dT P TC
n=2 Second Order Finite discontinuity G  H  T S
dG  VdP  SdT
 1 (G)  H   2 (G)  1  H  CP   (G) 
 1
 S    0  2 
    0   (T)    S
 (T) T TC TC  (T)  P TC  T  P TC  P

Second derivative is CP

 NO discontinuous changes in entropy, enthalpy & specific volume.

 NO latent heat of transformation
 High specific heat at the transition temperature
 Finite discontinuity in CP (NOT infinite)
 Lamda () Transitions (-point transitions) show infinity


 Concept of a metastable phase not readily applicable to a 2 transition →

single continuous free energy curve.
 Ferromagnetic ordering, Chemical ordering are examples of 2 transitions.

 In a two component system a 2nd order transformation requires equality of

entropy and volume of two phases + identical composition of the two
Quartz phases.
 2 transitions can be described by mean field descriptions
of cooperative phenomenon
 Order parameter continuously decreases to zero as T →
TC
 Any transition which can be described by a continuous
change in one or more order parameters can be treated by
a the generalized LANDAU Equation
Schematics

In a two component system:

 1st order transformation appears in a
phase diagram as two line bounding the
region where two phases (of different
composition) coexist.
 Second order transformation appears as a
single line.

Phase Transformations: Examples from Ti and Zr Alloys, S. Banerjee and P. Mukhopadhyay, Elsevier, Oxford, 2007
n=3 Third Order

 There is usually no classification as third order (II and higher order are clubbed
together)
 Superconducting transition in tin at zero field & Curie points in many
ferromagnets can be considered as third order transitions
Mixed Order
Landau Equation

 Close to the critical temperature:

The free energy difference (G) between finite and zero values of order
parameter () may be expanded as power series
 Practically, any physical observable quantity which varies with
temperature (or other thermodynamic variable) can be taken as a
experimental order parameter

G  G  finite  G  0  A 2  B 3  C  4 ... A, B, C.. = f(T, P)

n=1 First Order

G  A 2  B 3  C  4 ...
Not zero

Note the barrier

T  TC • Two minima separated by a G barrier

T  TC • T slightly less than TC the system still not unstable at  = 0 (state)

(curvature remains +ve)
 a gradual transition of the system in a homogenous fashion to a the
free energy minimum at  = C (or near it) is not possible
• Phase transition can initiate if localized regions are activated to cross the free energy barrier (beyond
 = *) → where phase with finite  can grow spontaneously
• Formation of localized product phase regions with  ~ C → nucleation

Sharp interface between parent and product phases

 Nucleation and Growth  Discrete nature of the transformation
n=2 Second Order G  A 2  C  4  C  6 ... • Only even powers
B0
• Single equilibrium at  = 0 → corresponds to +ve value of A
T  TC
• +ve curvature

• Curvature at  = 0 decreases
  2 (G) 
T  TC • System becomes unstable at Curvature at   0   2
T = TC and fluctuations will lead  ( )  0
to lowering of energy

T  TC • ve curvature at  = 0
→ corresponds to ve value of A

• Glass transitions, Paramagnetic-Ferromagnetic transitions

 Lambda transitions

 Heat capacity tends to infinity as the transformation temperature is approached

 E.g.: Transformation in crystalline quartz
Order-disorder transition in -brass (B2 → BCC, Cu-Zn alloy)
 Symmetrical -transition → Manganese Bromide

Manganese Bromide:
Quartz:
Symmetrical -transitions
Unsymmetrical -transitions
Homogenous (Continuous) Transitions

 Parent phase gradually evolves into the product phase without creating a localized sharp
change in the thermodynamic properties and structure in any part of the system
 The system becomes unstable with respect to small (infinitesimal) fluctuations → leading
to the transition
 The free energy of the system continuously decreases with amplification of such
fluctuations

USUALLY
• First order transitions are discrete (For T > Ti )
→ Nucleation and Growth
• Higher order transitions are homogenous
→ parent and product phase cannot be sharply demarcated at any stage of the transition

NO Sharp interface between parent and product phases

 Continuous nature of the transformation
For T < Ti
• First order transitions are can proceed in a continuous mode
• Not all first order transitions have a instability temperature
• Examples of first order continuous transitions (conditions far from equilibrium):
 Spinodal clustering
 Spinodal ordering
 Displacement ordering
Spinodal clustering Spinodal decomposition

 Phase diagrams showing miscibility gap correspond to solid solutions which

exhibit clustering tendency
 Within the miscibility gap the decomposition can take place by either
 Nucleation and Growth (First order) or by
 Spinodal Mechanism (First order)
 If the second phase is not coherent with the parent then the region of the spinodal
is called the chemical spinodal
 If the second phase is coherent with the parent phase then the spinodal
mechanism is operative only inside the coherent spinodal domain
 As coherent second phases cost additional strain energy to produce (as compared
to a incoherent second phase – only interfacial energy involved) → this requires
additional undercooling for it to occur
 Spinodal decomposition is not limited to systems containing a miscibility gap
 Other xamples are in binary solid solutions and glasses
 All systems in which GP zones form (e.g.) contain a metastable coherent miscibility gap
→ THE GP ZONE SOLVUS
 Thus at high supersaturations it is GP zones can form by spinodal mechanism
A coarsened spinodal microstructure in Al-22.5 at.% Zn-0.1 at.% Mg solution treated 2h at 400C and aged 20h at
100C. TEM micrograph at 314 kX. (K.B. Rundman, Metals Handbook, 8th edn. Vol.8, ASM, 1973, p.184.
 Nucleation & Growth Spinodal
The composition of the second phase remains A continuous change of composition occurs
unaltered with time until the equilibrium values are attained
The interfaces between the nucleating phase The interface is initially very diffuse but
and the matrix is sharp eventually sharpens
There is a marked tendency for random
A regularity- though not simple- exists both in
distribution of both sizes and positions of the
sizes and distribution of phases
equilibrium phases
The separated phases are generally non-
Particles of separated phases tend to be
spherical and posses a high degree of
spherical with low connectivity
connectivity
Spinodal Ordering
 Ordering leads to the formation of a superlattice
 Ordering can take place in Second Order or First Order (in continuous mode
below Ti) modes
 Any change in the lattice dimensions due to ordering introduces a third order
term in the Landau equation
G  A 2  B 3  C  4 ...
Not zero
 Continuous ordering as a first order transformation requires a finite supercooling
below the Coherent Phase Boundary to the Coherent Instability (Ti) boundary
 These (continuous ordering) 1st order transitions are possible in cases where the
symmetry elements of the ordered structure form a subset of the parent
disordered structure
 L+ L

Ordered solid
’
A  + ’
B
METASTABLE STATE
For a first order transformation the free energy curve can be extrapolated (beyond the
stability of the phase) to obtain a G curve for the metastable state

Liquid Metastable

Solid Metastable
G →

Solid stable Liquid stable

Tm

For a second order transformation the free energy curve is a single continuous curve
and the concept of a metastable state does not exist
Enantiotropic transformations
Equilibrium transitions: Reversible and governed by classical thermodynamics
 L → A (at the melting point: Tm = TL/A)
 A → B (at the equilibrium transformation T: TL/A)
 A → A’ (transformation between two metastable phases)
Monotropic transformations
Irreversible (no equilibrium between parent and product phases)
 A’ (metastable) → B (stable) (at T1)
 Supercooled liquid (metastable) → A (stable) (at T2)
Displacive transformation

 Changes in higher coordination effected by a distortion of the primary bond

 Smaller changes in energy
 Usually Fast
 High temperature form → more open, higher specific volume, specific heat, symmetry
 E.g.:  high-low transformations of quartz (843K), tridymite (433K & 378K), cristobalite
(523K)  SrTiO3
 Toy Model for Displacive Transformation

M.J. Buerger, Phase Transformations in Solids, John Wiley, 1951

 L+ L

L+ L
Ordered solid
’
 A B
 + ’

Ordered solid
’
A  + ’
B
 L
L+
E.g. Au-Ni


1 2
A 1 + 2 B