Fundamentals of Materials Science and Engineering: An Integrated Approach, 3e

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2nd Revised Pages

11.3 The Kinetics of Phase Transformations • 409

Surface or interface

Solid

Liquid



SL

IL

SI

Figure 11.5 Heterogeneous

nucleation of a solid from a liquid.

The solid–surface (γSI), solid–liquid

(γSL), and liquid–surface (γIL)

interfacial energies are represented

by vectors. The wetting angle (θ)is

also shown.

energy (i.e., energy barrier) for nucleation (G∗of Equation 11.4) is lowered when

nuclei form on preexisting surfaces or interfaces, since the surface free energy (γ

of Equation 11.4) is reduced. In other words, it is easier for nucleation to occur at

surfaces and interfaces than at other sites. Again, this type of nucleation is termed

heterogeneous.

In order to understand this phenomenon, let us consider the nucleation, on a

flat surface, of a solid particle from a liquid phase. It is assumed that both the liquid

and solid phases “wet” this flat surface, that is, both of these phases spread out and

cover the surface; this configuration is depicted schematically in Figure 11.5. Also

noted in the figure are three interfacial energies (represented as vectors) that exist

at two-phase boundaries—γSL,γSI, andγIL—as well as the wetting angleθ(the angle

between theγSIandγSLvectors). Taking a surface tension force balance in the plane

of the flat surface leads to the following expression:

γIL=γSI+γSLcosθ (11.12)

For heterogeneous

nucleation of a solid

particle, relationship

among solid-surface,

solid-liquid, and

liquid-surface

interfacial energies

and the wetting angle

Now, using a somewhat involved procedure similar to the one presented above

for homogeneous nucleation (which we have chosen to omit), it is possible to derive

equations forr∗andG∗; these are as follows:

r∗=−

2 γSL

Gv

(11.13)

For heterogeneous

nucleation, critical

radius of a stable

solid particle nucleus

G∗=

(

16 πγSL^3

3 Gv^2

)

S(θ) (11.14)

For heterogeneous

nucleation, activation

free energy required

for the formation of a

stable nucleus TheS(θ) term of this last equation is a function only ofθ(i.e., the shape of the

nucleus), which will have a numerical value between zero and unity.^1

From Equation 11.13, it is important to note that the critical radiusr∗for het-

erogeneous nucleation is the same as for homogeneous, inasmuch asγSLis the same

surface energy asγin Equation 11.3. It is also evident that the activation energy

barrier for heterogeneous nucleation (Equation 11.14) is smaller than the homoge-

neous barrier (Equation 11.4) by an amount corresponding to the value of thisS(θ)

function, or

G∗het=G∗homS(θ) (11.15)

(^1) For example, forθangles of 30◦and 90◦, values ofS(θ) are approximately 0.01 and 0.5,
respectively.