5-2 Glass transition, hydrous granitic systems.

Now look at this next plot.

It seems rather benign.
It's a plot of the glass transition temperature.
In this case, the glass transition temperature has been defined how?
It's been defined implicitly as a time scale.
Remember that I told you that we have a time-temperature relationship, which we call
the glass transition.
And in order to talk about a glass transition temperature, either everyone in the room
has to agree on a certain convention, implicitly, or it has to be stated explicitly.
The latter is perhaps better.
And so, what you see on the vertical axis here is an explicit statement about what glass
transition temperature am I speaking of.
I'm speaking of the one, which corresponds to a particular relaxation time, which, in
turn, corresponds to a particular shear viscosity, through the Maxwell relation as we've
seen previously.
And the shear viscosity that we've chosen is stated here very precisely at 10 to the 12.38
Pascal seconds.
Now if you look on the horizontal axis you see water content.
Now this is one of the first mentions that we make of significant water.
Water is the most common volatile substance in these melts.
We've mentioned that at the beginning of the course, and you can see here that the water
contents we're talking about are very, very substantial.
These are weight percents of water and they run up to many, many weight percent.
So it means that it is relevant in volcanic systems to concern ourselves with water
contents in silicate liquids, which run up to 3, 4, 5, 6 weight percent of water.
And, as we'll see later, the details of how these things oversaturate, when they're rising
to the surface before an eruption, is a large, large control on how volcanic eruptions
actually take place.
And one of the reasons that it's so sensitive that eruptive behavior really is sensitively
dependent on water content, is in essence given by this plot.
You see the glass transition temperature has a function of dissolved water content in the
melt.
And what you see is a very, very large vertical scale in temperature.
You see it running, in this case, it's temperature in degrees Kelvin over approximately
400 degrees, 400 degrees Kelvin or 400 degrees Celsius.
Now, that implies that we have started from a very very dry melt at the beginning at
zero weight percent of water.
In nature, nothing is completely dry, but nevertheless in a laboratory it's relatively easy
for us to bring the water contents down to a few ppm, which we can describe
approximately as dry.
And you can see the data points, which run from that dry value at the extreme upper left
of the diagram, where we're up near 1100 Kelvin, at the glass transition temperature.
That's a very high glass transition temperature.
And then, it runs down, it runs down fairly fast, fairly steeply, as we add the first couple
8% of water to the system.
And then, it begins to flatten out, such that, if I go beyond 5 weight percent of water in
this diagram, I will more or less have a very, very subtle drop in the further variation of
Tg.
Now, all of the data points that have been taken to produce this curve have come from
very different experiments.
And that's why I show it to you at this point in time.
This is a triumph, if you will, of the equivalence principle.
Because there are four different techniques from five different studies, which have been
plotted on this curve.
And as you see very clearly, they all lie fairly tightly on this curve.
There have been volumetric measurements of the relaxation of this system.
There have been measurements of the viscosity of this system, through the Maxwell
relationship to determine the relaxation time.
There have been measurements of the heat capacity to determine the peaks on the heat
capacity curve and, and we'll see more if it in a moment, there have actually been
measurements of the structural role of water through spectroscopy in these liquids,
which also can be used to give a reaction time or a relaxation time of spectroscopic
results of structure.
And all of these things: volume, enthalpy, viscosity and structure, completely different
experiments done in different labs by different groups around the world for different
purposes, not even for the purpose of determining Tg explicitly, when they are corrected
for the experimental timescales, the details of how long these experiments took to
perform, what temperature-time steps were involved, the details of this, when they are
made comparable, when you bring the timescales to a common value and you collapse
these points on a single curve as you see described here.
So two points here.
A demonstration that the equivalence runs across a wide range of techniques to
determine the glass transition temperature, four different properties, if you will.
And secondly, that water has an enormous effect on this value.
So water content in our samples is going to be critical for us to be able to parameterize
what is going on in relaxation time.
Here, a further example of this equivalence.
You see a very simple plot, where you have, vertically, the glass transition temperature,
which has been determined by picking the peak of calorimetric traces of a series of
glasses and you see on the horizontal diagram once again a determination of the glass
transition, which has been chosen based upon a constant value of viscosity.
And you see that these two curves more or less lie not only on a one to one slope, these
two sets of data, when I plot them versus each other lie on a one to one slope but you
also see that they, more or less, lie at equivalence.
And, that can actually be adjusted for any empirical comparison of calorimetric versus
viscous results for relaxation time, or for glass transition, simply by adjusting the
absolute value of viscosity to bring it into equivalence on the line.
So, to sum up, now, and to bring perhaps the last key feature into the equivalence
conversation, look at the following diagram.
You have to study it for a few moments, it has four axes.
It has two vertical axes and it has two horizontal axes.
The two horizontal axes are different temperatures expressed as the reciprocal or the
inverse of absolute temperature. an Arrhenius plot, as we call it.
And the vertical axes are, on the left-hand side. the (negative) or (the), the inverse minus
the log base 10 of the quench rate in degrees Celsius per second.
And you take that one and put it together with the bottom axis, which is the glass
transition temperature, as a reciprocal value.
And what you're looking at on the left and on the bottom is the variation in the glass
transition temperature observed, when I chance the cooling rate or the heating rate of
the observation.
So now we're bringing in a further parameter.
We're bringing in the heating rate during an experimental determination or the cooling
rate during a preparation or an experimental determination.
And we're plotting the glass transition that we observe as an absolute value of
temperature from the peak.
Okay.
Now, the upper scale, temperature, reciprocal temperature, and the right-hand scale,
which is the log of the viscosity, is simply a plot of the temperature dependence of the
viscosity of the system.
So, by overlaying these two curves, you see, clearly, that the temperature dependence of
the viscosity is identical in slope to the dependence of Tg, the glass transition
temperature on the heating-cooling rate of an experimental determination using
calorimetry.
So we simply slide those two plots into equivalence.
We overlay the two curves.
And it allows us to read from one scale on the left-hand side vertically, to the other scale
on the right-hand side.
And that gives us a relationship, which is expressed algebraically here.
Between the effective cooling rate or heating rate of an experiment to determine the
glass transition temperature and the viscosity, which is obtained at that glass transition
temperature.
Now that may not yet sound dramatic, but remember, if we have a relationship between
the viscosity of the glass transition temperature, and the cooling or heating rate to obtain
it, we also have the Maxwell relationship, which means we're one step away from, and
we take that step now.
We convert the shear viscosity into a relaxation time through Maxwell.
And if we performed this, then we have simply, linearly, a relationship now between a
very powerful relationship between the cooling effect of cooling rate or heating rate of
an experiment and an absolute value of the relaxation time available during the heating
or during the cooling.
This means that we will be able to plot heating and cooling rates on diagrams of
absolute relaxation time.
And we can compare scanning experiments, dynamic experiments, with static
experiments held at a particular temperature for a particular time.
And you see in the algebra presented here, that you simply transform from a logarithmic
sense, the relationship between the heating and cooling rate, and the viscosity at the
glass transition to one involving the relaxation time at the glass transition.