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Solidification of pure metal: Phase rule, Concept of Free Energy, Entropy, Surface Energy (grain

boundary) & under cooling, Nucleation & Growth, homogeneous & heterogeneous nucleation,

directional solidification

1. Estimate the size of critical nucleus of tin when it is super cooled by 20C. Assume nucleation to

be homogeneous. The enthalpy change for solidification of tin is 0.42 GJ/m

3

. The liquid / solid

interfacial energy is 0.055 J/m

2

. The melting point of tin is 232 C.

2. A metal under goes an allotropic transformation at room temperature at high pressure and at

lower temperature at atmospheric pressure. Is the volume change associated with this

transformation positive or negative?

3. Bismuth has a density of 9.8Mg/m

3

at room temperature. Its coefficient of linear expansion is

14.6x10

-6

/ C. The density of liquid metal at melting point (271C) is 10.07 Mg/m

3

. Find our

dT/dP and estimate its melting point at 100 atmosphere pressure. Latent heat = 10.9 kJ/mole

(atomic weight = 209)

4. Derive an expression for critical nucleus size as a function of temperature and show with the

help of a schematic graph its variation with temperature. Assuming that a stable nucleus should

have at least 100 atoms which correspond to around 1nm radius mark the region of

homogeneous nucleation.

Answer:

1.

0.42

0.0166 GJ/m

3

and Critical nucleus size =

.

.

3.3

2. The effect of pressure on transformation temperature is given by:

transformation be represented as

3. Let room temperature = 25C, volume increase due to temperature change =3T where , is

coefficient of linear expansion. Volume of 1gm mass at room temperature = 1/

0

& volume of

solid Bi at melting point = (1/

0

) + 3T. Therefore density of solid Bi at melting point =

= 9.7Mg/m

3

. On melting density increases V < 0.

..

..

=

-7.9x10

-7

m

3

.

.

.

25.31

10MPa. Therefore the change in melting point at 100 bar pressure = 2.53C.

4. Critical radius =

where H & S are enthalpy & entropy terms. Suffix v denotes per unit volume. At melting

at 300K & 10 atmosphere (say) (P1 & T1)

at 290K & 1 atmosphere (say) (P2 & T2)

H > 0 reaction is endothermic &

0

point (T

0

) f

v

= 0. Thus

&

H

v

is negative. Therefore

T0. As T approaches zero r* becomes exceedingly small since H

v

>> . This is schematically

shown as follows:

r

T T

0

1 nm

Homogeneous

nucleation

Liquid

No homogeneous

nucleation

Homogeneous nucleation

is possible below a

specific temperature T

c

T

c

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