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RTEP2015 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 110 (2016) 012018 doi:10.1088/1757-899X/110/1/012018

Determination of glass transition temperature for polymers by

methods of thermoactivation spectroscopy

V M Yurov1, V C Laurinas1 and E N Eremin2 and M S Gyngazova3

1
E A Buketov Karaganda State University
2
Omsk State Technical University
3
National Research Tomsk Polytechnic University, Tomsk, Russia
E-mail: [email protected]

Abstract. For rapid determination of glass transition temperature for polymers, we propose a
method of thermally stimulated luminescence. The experiments were carried for epoxy
polymers dyed and undyed with organic dyes. It is shown that glass transition temperature
depends on curing temperature and concentration of the dye. The comparison with the
thermogravimetric analysis showed coincidence of the results obtained.

1. Introduction
The glass transition temperature of polymers is an important characteristic defining their practical
application in a particular area [1–4].
The glass transition temperature of polymers is an important characteristic defining their practical
application in a particular area [1–4].
A large number of methods have been currently developed to determine the glass transition
temperature for polymers:
- Differential Thermal Analysis (DTA). In this method, when glass transition temperature is
attained, the slope of the specific volume of the sample temperature changes [5, 6];
- Single Differential Thermal Analysis (Single DTA), which combines both, DTA and
thermogravimetric method [7]
- Differential Scanning Calorimetry (DSC). This method measures the heat flow to/or from a small
sample, when the sample is subjected to a programmed temperature variation [2, 5, 8];
-Thermogravimetric Analysis (TGA). This method measures the change in mass of the sample in a
linear temperature change [5, 6, 8, 9];
- Evolved Gas Analysis (EGA). EGA is a family of methods to analyze the nature and amount of
volatile gaseous product evolving from the sample which is subjected to programmed temperature
variation. The most important methods are mass spectrometry and infrared spectroscopy. EGA is often
used in combination with TGA. [10];
- Thermomechanical Analysis (TMA). TMA measures deformation (typically one-dimensional
deformation) of the sample as a function of temperature. Different varieties of the method use the
mode of constant, increasing or modulated power. [11];
Dynamic Mechanical Analysis (DMA). In this method, the sample is subjected to sinusoidal
mechanical impact. The amplitude, phase shift, and other characteristics are the functions of
temperature [12–14];

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RTEP2015 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 110 (2016) 012018 doi:10.1088/1757-899X/110/1/012018

- and others.
Most of the methods described above demand for the realization of complex and expensive
equipment.
In this paper for the rapid determination of the glass transition temperature polymers, we propose a
method of thermoactivation spectroscopy.

2. Methods of thermoactivation spectroscopy (TAS)

The physical nature underlying TAS methods is implies that when the temperature of the sample
changes under a certain law, the transition from the nonequilibrium state to a new state approaching
the thermal equilibrium is thermally stimulated. This transition may be foolowed by thermally-
stimulated luminescence, TSL) [15]), by emission electron (thermally-stimulated emission of
electrons, TSE [16]), by the change in conductivity (thermally-stimulated conductivity [17]), etc. The
analysis of the temperature dependence for the changing physical property of an object allows
exploration of the parameters of electrically or optically active defects, mechanisms of relaxation
processes occurring in the substance.

3. Results and discussion

The experimental scheme in the TSL method is simple: the polymer was irradiated with the ultraviolet
deuterium lamp 400 W (any other source of ultraviolet radiation can be used) for 5–10 minutes at T =
80 K through the quartz window and a combination of light filters that produce the emission band
lamp with 300 nm. The temperature of the sample (1 mm thick and 10 mm in diameter) was measured
by the copper-constantan thermocouple one junction of which was mounted on the sample surface,
and the other one was placed in a Dewar vessel with melting ice. The sample was heated at a constant
rate of 0.15 K/s through a copper chip carrier via an electric heater. The integral emission of the
sample was detected by a photomultiplier tube and then the signal entered the input of the DC
amplifier and the display.
Figure 1 shows the integral curve of the thermally-stimulated luminescence for epoxy polymers
obtained under various curing temperatures: 100 ° C (1), 140 ° C (2), 200 ° C (3).

Figure 1. Thermally-stimulated luminescence of the undyed polymer produced under different

curing temperatures

2
RTEP2015 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 110 (2016) 012018 doi:10.1088/1757-899X/110/1/012018

The corresponding curves in Arrhenius coordinates (lnI ~ 103/Т) intersect the horizontal axis at
points with temperatures TCl , TC 2 , TC3 . Table 1 shows these values along with the results of the
thermogravimetric analysis.
Fig. 2 shows the integral curve of the thermally-stimulated luminescence of the epoxy polymer
dyed in yellow with rhodamine of different concentration.

Figure 2 Thermally-stimulated luminescence of the dyed epoxy polymer

Table 1. Glass transition temperature for epoxy polymer

Sample Method TC1 (К) TC 2 (К) TC3 (К)

Undyed TSL 471.6 446.4 423.7

epoxy polymer
TGA 479 450 426

Epoxy polymer TSL 400 383 379

dyed with
rhodamine 6Y TGA 406 392 384

The data provided in the Table 1 show:

1) the values of the glass transition temperature Tc obtained by the method of thermally stimulated
luminescence are in good agreement with the thermogravimetric measurements, which allows its
application to determine Tc along with conventional methods;

3
RTEP2015 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 110 (2016) 012018 doi:10.1088/1757-899X/110/1/012018

2) the glass transition temperature Tc of the polymer produced under different curing conditions
varies considerably (in this case, almost by 50 K), which allows the use of the method of thermally
stimulated luminescence as a rapid method when developing the polymer production technology;
3) the glass transition temperature Tc of the polymer decreases when its base is doped with dye
molecules (up to 70 K in this case), and as the concentration of the latter grows, it continues to
decrease.

4. Conclusion
With no regard to the issues related to the mechanism of excitation of thermally stimulated
luminescence in undyed and dyed epoxy polymers after exposure to UV radiation, it should be noted
that the method of thermally stimulated luminescence in its sensitivity is significantly superior to
optical absorption techniques, electron paramagnetic resonance and other spectroscopic methods. It is
sufficiently simple, reliable and does not require expensive equipment.
In our opinion, further investigation of the method with other types of polymers will provide engineers
with a simple method to control the production technology of polymer materials with desired
properties.
Acknowledgements
This work was financially supported by The Ministry of Education and Science of the Russian
Federation in part of the science activity program.

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