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Measurement of the Glass Transition Temperature Tg

Determination of the glass transition temperature, Tg, by dilatometry:

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Figure 1: Determination of Tg by dilatometry (click image to enlarge). The linear sections below and
above Tg are marked green; Tg is the temperature at the point of intersection of the corresponding red
regression lines.

Tg may be derived from the thermal expansion curve as demonstrated in Figure 1. It is not clearly
defined, however, how the slope changes and the green marked linear sections should be found. It is
necessary to rely in a reasonable personal judgement.

Determination of the glass transition temperature by DTA/DSC:

For most Tg values in the literature the DTA/DSC technique is used. The following paragraphs are taken
from a paper by Mazurin & Gankin (2007) about the subject:
Probably everybody agrees with the statement that Tg is one of the temperatures within a glass transition
region where the metastable melt transforms into glass in the course of its cooling and where glass
transforms into metastable melt in the course of heating. The exact value of Tg is determined by
analyzing the temperature dependence of a property. To do this some scientists use cooling curves.
However, the overwhelming majority of scientists prefer to use solely heating curves. Below we will
consider the results of analyzing of only these kinds of heating curves.
Figure 2 shows three different points on the curve of temperature dependencies of specific heat that can
be used to determine Tg. In more than 300 DTA/DSC studies of Tg published over a period of 2005-2006
the authors specified the way of Tg determinations only in 68 publications. 70% of these authors used
point A, 20% point B and 10% point C. In about 250 papers (out of 300) the way of Tg determination was
not specified. At the same time, as is seen from the caption to Figure 2, the difference between these
three values of Tg is quite great. It seems obvious that to standardize Tg determination it is necessary to
select the most popular way of processing DTA/DSC curves, namely, the intersection of two tangents at
the start of the corresponding endotherm (point A).
Figure 2: Various points in temperature dependencies of heat capacity used to determine Tg. The values
of log(η(Tg), Poise) for these points in the case of commercial soda-lime-silica glasses (in the
temperature range of 500- 580°C viscosity was calculated by the equation log(η(Tg), Poise) = -22.56 +
28200/T where T is the absolute temperature): A: 13.20; B: 12.36; C: 11.56. The calculations were done
for heating rate of 10 K/min and for glass samples initially cooled from the temperatures well above Tg at
the same rate.

It is well known that the values of Tg depend both on heating rates and rates of cooling of samples prior
to measurements (Mazurin, 2007). The ratio of cooling and heating rates has also an influence on the
shape of DTA/DSC curves, which in its turn influences the reproducibility of the results obtained. The
optimum results are obtained in the cases when an initial cooling rate is equal to a heating rate (see, for
example, Moynihan et al., 1974). There are many cases when samples used for measurements were
preliminary annealed using a certain arbitrarily selected schedule. In these cases it is practically
impossible to predict the result, except that the deeper the annealing, the lower the log(η(Tg)) value.
To obtain Tg values compatible with each other (i.e. the values that will allow for the joint use of data of
numerous authors in order to find general composition dependencies in wide composition ranges) it is
necessary to select a certain standard heating rate for all experiments. The analysis of the experimental
data on Tg published in 2005 shows that 75% of investigators specifying heating rates for DTA/DSC
measurements selected 10 K/min. It should be taken as a standard heating rate. Correspondingly, the
rate of initial cooling should also be equal to 10 K/min. For dilatometric measurements of Tg, however,
standard cooling/heating rates within the range of 3-5 K/min should be used. In this case, Tg values
obtained by DTA/DSC and dilatometric methods will be approximately compatible with each other. This
statement was substantiated in some details by Mazurin (2007).
One of the main obstacles to the efficient use of Tg data is the fact that in more than half of all papers
containing Tg data it is impossible to find information required for a proper application of such data. As
follows from Figure 2 and Mazurin (2007) for samples of the same glass a possible range of changes in
log(η(Tg), Poise) can be found between ~14.0 (determination of Tg by version A for quenched samples
heated at the rate of 3 K/min) and ~10.0 (determination of Tg by version C, for well annealed samples at
the heating rate of 40 K/min).

If a scientist wants to publish Tg data that could be used efficiently by other scientists, it is necessary to
follow several quite simple recommendations: (1) to use version A for determination of Tg (see Figure 2);
(2) to select a heating rate equal to 10 K/min in DTA/DSC studies and 3-5 K/min in dilatometric studies;
(3) to cool the samples used for measurements from a temperature well above Tg at the rate equal to a
heating rate in the course of measurements; (4) to specify the above three features of the experiments in
the a paper to be published.

Mazurin (2007)
O. V. Mazurin; Glass Physics and Chemistry, vol. 33, 2007, p 22.
Mazurin & Gankin (2007)
O. V. Mazurin, Yu. V. Gankin: "Glass transition temperature: problems of measurements and analysis of
the existing data"; Proceedings, International Congress on Glass, July 1-6, 2007, Strasbourg, France.

Moynihan et al. (1974)

C. T. Moynihan, A. J. Easteal, J. Wilder, J. J. Tucker; J. Phys. Chem., vol. 78, 1974, p 2673.