Welcome back.

In this lesson we're going

to be describing the concept of the driving force. Let's take the simple concept
that
we have introduced previously. We're going to be looking
at a pure substance. And remember that a pure
substance is a material that melts at a single temperature for
a fixed pressure. I've indicated on this diagram
that's up on the screen, two phases. A blue which represents the solid, and the
red, which represents the liquid state. And what we've done is to plot them
in a way such that their behavior reflects the behavior of the change in
free energy of each of the two phases. Now, one of the things that's important
is that, at the equilibrium melting temperature, the free energy of the two
phases are equal to one another. So that point becomes fixed. In addition, when
we look to
the right of the melting temperature, that is to higher temperatures, what we wi
ll see is that the phase that
is the stable phase is the liquid phase. And you can see that and notice that by
recognizing that
the free energy of the liquid lies below the free energy of the solid,
which is represented by the blue line. Now, when we take a look to the left, wha
t we're now looking at is the stability
of the microstructure, which is the solid. And what we see, of course, is that
the blue line lies below the red line, meaning that we have a stable
microstructure in the case of the solid. I've also indicated the term delta T,
which represents undercooling. And we talk about undercooling, it's the
temperature below the melting temperature. So when we define delta T in this way
,
what we're actually saying is below the equilibrium melting temperature,
the undercooling, delta T is positive. Now, we start out with the free energy
of the two phases being equal at the equilibrium melting temperature. And as a c
onsequence of that,
the change in free energy associated with a particular
volume of material for the liquid to solid change is
going to be equal to zero. And what we can do is we can substitute
that into the entropy relationship. And basically what it says on the left
hand side is that the entropy when we go form the liquid to the solid is going t
o
be equal to the change in the enthalpy for that process divided by
the equilibrium melting temperature. Now one thing we should point out here
is if we look at the signs of the two expressions, the one on the left and
the one on the right. In the case of delta V for entropy, we know that the entro
py of the solid
is below the entropy of the liquid. Therefore that term is
going to be negative. And what that implies is what has to
be true on the right hand side is that the delta H of liquid going to
solid must be also negative, which means we're dealing
with an exothermic reaction. So the solidification,
or the development of a solid phase from a liquid is
going to be an exothermic process. Now what we can do is we can take
a look at any temperature now and consider what the free energy would be. And th
e way we're going to do this is
to assume that the heat capacities of the solid and the liquid are the same. Tha
t's just the simple approximation
that we can use in the vicinity of the melting temperature. When we do that, and
we substitute that
into our Gibbs free energy equation, which relates the free energy
to the enthalpy and the entropy. What we wind up is that the change in
free energy of liquid going to solid per unit volume is going to be proportional
to the change in the enthalpy divided by the melting temperature,
times the amount of undercooling. So, those terms, delta H per volume, divided b
y TM,
those are all positive terms. And what we have with respect
to the positive undercooling is another term which is positive. So what that is
in effect doing is
it's showing us that the free energy change of liquid going to solid is going
to be negative, or hence, exothermic. And it's going to be controlled
by the value of delta T. Again we take a look at the two phases,
the liquid and the solid. And when the liquid is cooled
from below the equilibrium melting temperature there's
a driving force for solidification, and that's indicated by the red circle. So g
oing from the liquid
to the solid phase, the more material we transform,
the lower that free energy will become. And so we can see how that behaves with
respect to the change of going from solid to liquid. Now, when we take a look at
what
happens when we go to the solid phase, we're in a condition where the solid
has a lower free energy than does the liquid phase, and
that's what's driving the reaction. So homogeneous nucleation, and what we
mean by the term homogeneous is the fact that this process is going to be occurr
ing
randomly throughout the structure. So it's not going to occur specifically
at interfaces like the mold wall that separates the exterior from the
interior liquid that's being solidified. So what's happening then is that
the solidification process is occurring throughout the liquid, but
it's occurring in a random way. We'll be describing more of this
as we go further into this module. Thank you.