Phase Transformation and Gibbs free energy

Solidification
solidification of metals and their alloys is an important industrial process . Solidification happens in 2 stages: nucleation and growth

Nucleation and growth

Nucleation is the appearance of very small particles (nuclei) of the new phase ( consisting of a few hundred atoms) which are capable of growing .During the growth stage these nuclei increase in size, which results in the disappearance of some (or all) of the parent phase

Nucleation and Gibbs free energy

Homogeneous Nucleation depends on Gibbs free energy . Assume that each nucleus is spherical in geometry and has a radius r.

Total free energy depends on 2 factors : 1st is volume free energy which is the free energy difference between the solid and liquid phases, and because the volume is spherical the volume free energy is :

2nd energy is surface free energy (depends on surface tension ) this energy results from the formation of the solidliquid phase boundary during the solidification transformation and it is positive

Finally, the total free energy change of these two energies

is equal to the sum

*Surface free energy increase with radius squared (positive value) *volume free energy decrease with third power of radius (negative value) Total free energy increase at first then after reaching the critical radius point it decrease

Why

behave this way (increasing then decreasing)? In a physical sense, this means that as a solid particle begins to form as atoms in the liquid cluster together, its free energy first increases. If cluster reaches size corresponding to r* , then growth will continue with the decrease in free energy On the other hand, a cluster of radius less than the critical will shrink and redissolve .

is function in one variable (r) we want to know the value of (r*) take first derivative of then equate it with (0) which lead to :

*Volume free energy depend on temperature

latent heat of fusion Temp. in Kelvin *substituting in (r*)

melting temp.

this shows dependence of nucleation on temp.

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