Phase

Phase Content Transformation

Transformation 1.0 Introduction
2.0 Homogeneous Nucleation
2.1 Gibbs Free Energy
2.2 Energies involved in
homogeneous nucleation
2.3 Critical radius & Critical free
energy
by 3.0 Nucleation rate
4.0 Heterogeneous Nucleation
Dr.Srimala 4.1 Energies Involved in
heterogeneous nucleation

2.0 Homogeneous Nucleation

1.0 Introduction

Phase transformation proceed by Homogeneous nucleation occurs when there are no special objects
nucleation followed by its growth. inside a phase which can cause nucleation.

Nucleation can be divided into 2

For instance when a pure liquid metal is slowly cooled below its
types: equilibrium freezing temperature (undercooling) to a sufficient
degree numerous homogeneous nuclei are created by slow-moving
1. Homogeneous nucleation atoms bonding together in a crystalline form.
2. Heterogeneous nucleation

1
 2.1 Gibbs Free Energy 2.2 Energies Involved in Homogeneous
Nucleation

G = U - TS Homogeneous nucleation needs undercooling to get G for formation of new phase

Where U = Internal Energy, (energy)
T = Absolute Temperature, and
S = Entropy
Volume free energy surface energy
• Materials Scientists refer to the difference in G between the old and
new phases as the “ driving force” for the phase transformation. Assume that the new, product phase appears as spherical particles upon solidification

• The release of heat when a metal solidifies indicates that the

crystalline phase has a lower Gibbs Free Energy, G, than the liquid. 2r Free energy released by transformation is proportional
to the volume of the particle multiplied by the volumetric
free energy,  G B
• At the equilibrium freezing temperature the Gibbs Free Energy of the
liquid and the crystalline phase are equal. 4
Gvol   r3GB
3

Free energy consumed by creation of interface is proportional to the surface area

of particle and the interfacial energy, .
 G B volumetric free energy is actually the free energy change per
unit volume Gs  4 r 2
Note: G B  H  TS
Therefore, net change in free energy per particle,
H  T   T 
G B  H  T  H 1    H   approximately
To  To  To 4
  Gr   r 3GB  4 r 2
3

Negative, and represent involves the increase in

Note: the decrease in free energy energy required to form
a upon solidification a new surface

3
If a cube, volume free energy = Gvol  Gva

Surface energy = Gs  6 a2

2
Schematic diagram of the energies involved in homogeneous nucleation 2.3 Critical radius & Critical free energy
Retarding energy
The radius at which the free energy curve is at maximum is called critical
radius r* and the critical Gibbs energy corresponding to the r* is G*.
surface free-energy change
Gs  4 r2  G r
0
r
GT Total free-energy change Differentiate to find the
free-energy change (G)

Free Energy Change Gr

stationary point (at which
the rate of change of free
energy turns negative).

particle radius (r) r

Driving energy Volume free-energy change

4
Gvol   r3Gv
3

G r Replace r* in the following equation to obtain critical free energy.

0
r 4
Gr   r 3  G B  4 r 2 
3
From this we find the critical radius and critical free energy.
3 2
4  2   2 
Gr      G v  4    
8 r   4  r 2 G B  0 3   G B  G B 
4 r 2 G B   8 r  16  3
Gr 
3 G B 2
r2 8 2
 
r 4  G B GB 16  3
G* 
2 3 GB 2
r*  
G B

3
 In the case of transformation in condensed phase, the collision frequency at the
3.0 Nucleation rate nucleus interface expressed as follow :

Although we now know the critical values for a nuclei to become a nucleus, we do  GM 
v  vo exp
not know the rate at which nuclei will appear in a real system.
 kT 
To estimate the nucleation rate we need to know the concentration of nuclei of the vo is the jump frequency of the atoms or molecules to the surface of nucleus and
critical size and the rate at which such nuclei are formed. ∆GM is the activation energy for the movement to the nucleus

Concentration of critical nuclei, Cr is given by a Boltzmann factor, where C0 is the   Gr   G M 

number of atoms per unit volume (NA/V): N  vo ns C o exp    exp  
 kT   kT 
 Gr 
C r  C o exp  
 kT 
The rate of nucleation is determined by the concentration of nuclei of the critical
 GM 
exp  
size and the rate at which they are activated through the addition of atoms or  kT 
molecules to their surfaces.
N  vn s C r
 Gr 
ns is number of atoms or molecules to their surfaces. exp  
v is collision frequency of molecules with nuclei  kT 

Summary of nucleation rate: 4.0 Heterogeneous Nucleation

Heterogeneous nucleation occurs when there are special objects inside a
 G r   GM  phase which can cause nucleation.
N  v o n s C o exp    exp   kT 
 kT example : grain boundaries
triple junctions
Free energy dislocations
 Gr  GM 
N  K v exp    of critical (existing) second phase particles
 kT nucleus
 Gr  G M  Gr  GB (volume of cap) GS
N  v s * p d exp   
 kT Activation  = contact angle
Nucleation energy
rate (generally
Liquid
Vibration Density (no taken as
frequency of atom/vol) small

Solid
No of atoms Probability
at nucleus factor
k =1.38 x 10-23 J/K Nucleating agent

4
 4.1 Energies Involved in Heterogeneous
Nucleation
The surface energy term is derived as follows:

In the case of a heterogeneous nucleus in the form of spherical cap, the

surface energy term involves the surface energy between the solid Solid-liquid surface  2  r 2 1  cos  
nucleus and the liquid, and the change in surface energy of the catalyst
surface as it is coated by the nucleus.
Catalyst-solid surface 
  r 2 1  cos 2  
 s-l
liquid
Where r is the radius of curvature of the nucleus. Then we write

Solid  
 G surface  2 r 2 1  cos   s  l   r 2 1  cos 2   c  s   c  l 
r   c-s 
2R  c-l  s l  Solid-liquid interfacial energy
 cs  Solid-catalyst interfacial energy
 c l  Liquid-catalyst interfacial energy
Catalyst surface

Liquid-catalyst interfacial energy term can also be expressed as Volume in terms of its radius of curvature and contact angle is :
 3
 c  l   c  s   s  l cos   3  2  3S  S 
V  r  
 3 
Therefore,
Gr  GB ( volume of cap)  GS
 
Gsurface  2r 2 1  cos   s  l  r 2 1  cos 2   c  s   c  l 
 4 3
  2  3S  S 
Gr  GB r 3  4r 2 s l  
Gsurface  2r 1  cos   s  l  r 1  cos   c  s   c  s   s  l cos  
2 2 2 
 3   4 
Gsurface  2r 2 1  cos   s  l  r 2 1  cos 2    s  l cos   G r
0
r
Assume cos  S 8 r   4  r 2 G B  0
2
Gsurface  2r 1  S  s  l  r 1  S2
 2
  s l S  4 r 2 G B   8 r 
Gsurface  r 2 2  2S  s  l   s  l S   s l S 3  2
r2 8 2 r*  
 
Gsurface  r 2 s  l 2  3S  S 3   r 2 s l 2  3 cos   cos 3   r 4  G B GB G B

5
 As for solidification, the radius of the spherical caps depends only on the
Gr  GB ( volume of cap)  GS interfacial energy, so:
2 s  l
r*  
3
 4   2  3S  S 
Gr  GB  r 3  4r 2 s  l    G v
 3   4 
 3 2   2  3S  S 3  But the shape factor modifies the critical free energy:
4  2   2 
Gr  GB       4     s l   
 3  GB   GB    4 
  16  s3 l
G *  f ( )
 4  2 
3
 2 
2   2  3S  S 3  3  G 2v
Gr  GB       4     s l   
 3  GB   GB    4 
 
 f ( )
16  s  l 3  2  3S  S 3  90o 0.5
Gr   
3 G B 2  4  60o 0.16
30o 1.3 x 10-2
16  s  l 3  2  3S  S 3   2  3S  S 3 
G *    G het=G hom  
10o 7.0 x 10-4
3 G B 2  4   4 

Solution 1.1
Exercise 1.1
4
 G vol   r 3 G v
Take 108 J/m3 as a typical value of chemical (volumetric) free energy
3
change for formation of second phase particle and 1 J/m2 as surface 4
 G vol   r 3 (10 8 )
energy change. Calculate the radius of the spherical particle for which 3
surface energy is 1% of the volume free energy.
Gs  1
 G s  1  0 . 01  G vol
(1)  0 . 01[( 4 / 3 r 3 )(10 8 )]
r

6
 Exercise 1.2 Solution 1.2
T
a) Show that for T~Tm,  G   H (1  ) where H is the enthalpy
change on solidification per unit vol. T M (a) G  H  TS
H
G  H  T
b) For the solidification of a metal (Tm =1000 K) with undercooling of TM
200K, calculate the rate of homogeneous nucleation in Nuclei/m3/s. T
Neglect activation energy. Assume v = 1012/s and s*pd estimated as  G   H (1  ) proven
1028/m3 , H = -1.26x109 J/m3, LS=0.16J/m2 TM

T
(b) G  Gv  H ( )
TM
9 200 8 3
 G v  (  1 . 26 x 10 ) ( )  2 . 52 x 10 J/m
1000

16  3
G * 
3  G 2v
Quiz 1
16  ( 0 . 16 ) 3
G *   1 . 08 x 10 18 J At one atmosphere pressure pure
3 ( 2 . 52 x 10 8 ) 2
germanium melts at 1232 K and boils at
 G *  G A 
N  v s * p d exp    2980 K. The pressure at the triple point
 kT
 G * 
(S,L,G) is 8.4 x 10-8 atm. Estimate the
N  v s * p d exp   heat of vaporization of germanium.
 kT 
1 . 08 x10  18
N  10 12 . 10 28 exp  [ ]
(1 . 38 x 10  23 )( 800 )
N  10 40 . exp  ( 97 . 83 )
N  3 . 3 x 10  3 nuclei/m 3
/s

7
Liquid-catalyst interfacial energy term can also be expressed as Class Activity
THERMODYNAMICS-SNAKE & LADDER

The volumetric Gibbs free energy change is the product of the volume of the cap
and  G v , the specific Gibbs free energy change.

Volume in terms of its radius of curvature and contact angle is :

2
4 3  2  cos  1  cos   
V  r  
3  4 
4 3  2  cos  1  cos  2 
 G vol  r  G v  
3  4 
4 3
 G vol   r  G v f ( )
3

Class Activity
• 07 – A VOLUNTEER IN CLASS RULES
• 12 – GOOD MARKS IN EXAMS • 2 - 4 PLAYERS
• 16 – CONCENTRATES IN CLASS
• THROW THE DICE TO START THE
• 20 – SLEEPS IN THE CLASS
GAME.
• 34 – SUBMITS TUTORIAL
ON TIME • LADDER – ANSWER THE
• 40 – ALWAYS ASK LECTURER QUESTION. IF IT’S CORRECT,
• 50 – TALKS IN THE CLASS MOVE UP. IF IT’S WRONG, STAY
PUT.
• 55 – NOT DOING EXERCISES
• 62 – ESCAPES FROM CLASS • SNAKE- ANSWER THE QUESTION.
IF IT’S CORRECT, STAY PUT. IF IT’S
WRONG, SLIDE DOWN.
E.g.: What do you know about phase
transformation??
Answer: Any answer that is relevant
is CORRECT..Congratulations!!!