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APL 102

Phase transformations in Materials

Concepts: Driving force (solidification), Heterogeneous nucleation, nucleation rate

Lecture 39
 Recap
IIT Delhi Phase transformations
The phases present in a material may undergo change as a function of temperature and
pressure. Such changes are called phase transformations
G as f(T)
Solidification process

Decrease in Gibbs free energy

Homogeneous & Heterogeneous

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Formation of critical nucleus Atoms surrounding
by statistical fluctuation the critical particle

Critical
particle

Diffuse jump of a
surrounding atom to the
critical particle makes it a
nucleation
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Question for thought

What do the f * or r* depend on?

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Dependence of f * on temperature

One assumption would be that close to melting point latent heat of fusion
(Δh) and change in entropy (ΔS) do not vary much with the temperature
 Driving force for solidification
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g  g S  g L g (T )  h(T )  Ts (T )

g (Tm )  h(Tm )  Tm s(Tm )  0

h(Tm )
s (Tm ) 
Tm
g
h(T )  h(Tm ) s (T )  s (Tm )
g (T)
g (T )  h(Tm )  Ts(Tm )

h(Tm )
 h(Tm )  T
Tm
Tm  T
 h(Tm )
gL gS Tm
T
T Tm T g (T )  hm
Tm
 f 4
IIT Delhi f   r 3 g + 4  r 2 g
3
f1*
4 3
f (T )   r g (T ) + 4  r 2 g
f2* 3
r2 * r1 * r
T
g (T )  hm
Tm
T2 < T1
2g 2 g Tm
r*   r*  
g T hm
16  g 3 16  g 3Tm2
f *  f * 
3 (g ) 2 3 (T ) 2 (hm ) 2
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Tm

Decreasing f*

Decreasing r*
f →

r →
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Question for thought

As the degree of supercooling increases, do the nucleation

rate as well always increase?

No, because the thermal energy decreases and this control the nucleation rate
 Heterogeneous nucleation
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Nucleation is often aided by some preexisting surfaces, e.g., container

walls, inclusions, grain boundaries etc.

Such nucleation is called HETEROGENEOUS NUCLEATION

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
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Consider the nucleation of  from L on a wall of the container 

Interfacial Energies
L gL
 Alens gL
 Created

gL g
Created Acircle g

 g L  g  Acircle gL
Cos  Lost
g L

Surface tension force balance g L Cos + g   g L

Δf het  (Vlens )g + (A lens )g L + ( Acircle ) g   ( Acircle ) g L

Vlens = h2(3r-h)/3 Alens = 2rh h = (1-Cos)r rcircle = r Sin

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Similar to homogenous nucleation…

df het
0
dr

2g L
r *
hetero 
g Note that only one interfacial energy is coming along
with the contact angle

4 g L
3

f hetero
*
 
3 g 2
2  3 
Cos  + Cos 3
 
Comparison between homogenous and heterogeneous sites

f hetero
*

1 *
4

f homo 2  3Cos + Cos 3 
 Effect of contact angle
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1
f*hetero / f*homo →

f*hetero (0o) = 0
f*hetero (180o) = f*homo
no barrier to nucleation
0.75
no benefit
f*hetero (90o) = f*homo/2
0.5
g L  g 
Cos 
0.25 g L
Complete wetting Partial wetting No wetting
0
0 30 60 90 120 150 180
 (degrees) → Product phase is not
interacting with surface
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Artificial
Rain

by
Cloud
Seeding
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Question for thought

Recall grain refinement methods

Solidification was one method!
How heterogeneous nucleation can help in reducing grain size?
 Announcement
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 Impact energy lab location (Next Week Lab):

- Room No.:136, Block IV, Strength of Materials Lab

 NO Classes next week: 7th, 8th and 10th November.

Next Saturday (11th Nov.) works with Friday timetable.
Will inform over email if class will be held on 11th Nov.! No lab on that day!

 Buffer lab: E-mail request to be given by 8th Nov.

- Will happen in the last week (13th to 16th Nov)
- only for students who missed due to medical/emergency reasons

 Updated Lab marks & Minor 1 & 2, Quiz 1 & 2 marks:

Will be uploaded by 8th Nov. Last date for informing discrepancies 13th Nov.
E-mail with a picture of the mark (subject: Re: APL 102…)