Phase Transformations

Objectives of the class:

Principles f S lidifi i P i i l of Solidification Homogeneous nucleation Heterogeneous nucleation Examples of nucleation p

Solidification of Metals
The solidification of metals and their alloys is an important industrial process. Not l do t N t only d structural alloys start with the t l ll t t ith th casting of ingots for processing into reinforcing bars or structural shapes but shapes, when a metal is welded a small portion of metal near the weld melts and resolidifies. It also serves as a model to represent first order phase transformations in general. p g

Schematic Representation of Solidification

(a) Formation of stable nuclei (b) Growth of crystals (c) Grain structure

Homogeneous Nucleation
Homogeneous nucleation occurs when there are no special objects inside a phase which can cause nucleation. For instance when a pure liquid metal is slowly cooled below its equilibrium freezing temperature to a sufficient degree numerous homogeneous nuclei are created by slow-moving atoms bonding together in i a crystalline form. lli f

Typical Data Relevant to the Solidification of Metals

Gibbs Free Energy

G = U - TS where U = I t h Internal Energy, T = Ab l t T lE Absolute Temperature, t and S = Entropy Materials Scientists refer to the difference in G between the old and new phases as the driving force for the phase transformation. The release of heat when a metal solidifies indicates that the crystalline phase has a lower Gibbs Free Energy, G, than the liquid. gy, , q At the equilibrium freezing temperature the Gibbs Free Energy of the liquid and the crystalline phase are equal. t lli h l

Energies Involved in Homogeneous Nucleation

(1)Volume free energy (1)V l f 4 3 r Gv 3

(2) Surface energy

4 r2

Energies Involved in g Homogeneous Nucleation

Critical radius
4 3 2 G = r Gv 4 r 3
To find the minimum

d (G ) =0 dr
2 r* = G

Critical Radius of Nuclei g vs. Undercooling

Why you should eat the whole container of Ben and Jerry once you open it

Grain coarsening

Minimization of the surface energy (less surface)

Why should you eat the whole chocolate bar once you open it?
I dont know. Consult your local weight watchers

Heterogeneous Nucleation
Heterogeneous nucleation occurs when there are special objects inside a phase which can cause nucleation.

Danger of heating a hot water t

How to be an effective rain maker

Your problem: ots o c ouds o a Lots of clouds but no rain
The cloud problem: Lots of small spherical water droplets too light to fall under gravity

The droplet problem: The droplets need to freeze to ice which becomes a nucleus capable of attracting water vapor. In cold days it snows and In hot days it rains.

How to be an effective rain maker (2)

The ice problem: The homogeneous nucleation temperature is 40 C (way too cold) The solution (finally!!): Heterogeneous nucleation How to do it? Air Pollution will provide the seeds (O not the best solution) (OK, ) Use silver iodide crystals y decrease from -40 C to 4 C (not bad)

Homogeneous vs. Heterogeneous Nucleation N l ti

The critical radius, r*het, of a * f heterogeneous nucleus is much larger than the critical radius, r*hom, of a homogeneous Crystal radius nucleus of the same phase. For the same critical radius the heterogeneous nucleus contains far fewer atoms.

heterogeneous

homogeneous

Absolute temperature

A bubbly example
Carbonate drinks have carbon dioxide which is dissolved under pressure. When the can is opened the pressure drops and the gas comes out of solution in the form of bubbles. Aluminum and glass are poor catalysts for heterogeneous nucleation. Chalk on the other hand hand