Kinetic study of the polymerisation and thermal decomposition of DGEBA epoxy systems

A. Marcilla, F. Valds and J.C. Garca-Quesada CHEMICAL ENGINEERING DEPARTMENT UNIVERSITY OF ALICANTE, 03690 S. VICENTE DEL RASPEIG, ALICANTE, SPAIN.

ABSTRACT
DGEBA (diglycidyl ether of bisphenol A) epoxy systems are, probably one of the most common used for the production of matrixes in composites for high performance applications, due to their good mechanical properties, chemical and environmental resistance. These properties makes them suitable for purposes as aircraft components or boats construction. In this kind of systems a resin (in this case derived from DGEBA) is mixed usually with amine hardeners in stoichometric ratios to yield a low viscosity mixture easy to process and cure at temperatures ranging from 5C-150C, depending on the curing agent. When curing occurs, the liquid becomes progressively more viscous until it reaches a solid state, known as gel point where no more flow is possible. After gelling, the system can continue hardening until it reaches an optimum on its properties. The aim of the present work is the study of polymerisation kinetics and thermal behaviour of epoxy systems based on DGEBA and the hardener MTHPA (Methyltetrahydrophthalic Anhydride). Polymerisation kinetics and degradation processes of mixtures with different ratios resin/hardener have been monitored simultaneously by Differential Scanning Calorimetry, DSC and Thermogravimetric Analysis, TGA. Thermogravimetric analysis has been employed in two different types of experiments: 1. Single dynamic experiments at constant heating rate of liquid mixtures of different proportion of resin and anhydride. As it is possible to observe in Figure 1, strong differences concerning degradation velocity and temperature of the system are produced depending on its composition. As expected, pure chemicals are lost at low temperatures, and present a complex decomposition pattern at high temperatures. When the hardener is mixed with the resin, its evaporation is hindered by the polymerisation reaction that fixes it to the sample, and only a small shoulder can be observed at temperatures up to 150C (which according to DSC curves takes place at this temperature). After that step, and depending on the hardener/resin ratio a stable stage, associated to the polymer generated, is observed. Latter on, the polymer undergoes its final degradation originating a solid residue at temperatures up to 600C, with a yield that changes drastically with the above mentioned ratio. It is apparent that very useful information can be obtained from this type of experiments in all the stages of the process. The complexity of the system increases when mixtures with resin excess are studied as DSC curves for such systems reveal, since two exothermic peaks (one at lower temperatures due to resin-anhydride polymerisation and other at higher temperatures due to resin homo-polymerisation) are observed apart from the endothermic peaks corresponding to degradation processes of the different products produced. 2. Series of dynamic experiments, where liquid mixtures with the stoichometric ratio were cured at different controlled heating rates (10-35 C/min) until 220C to ensure the completion of the reaction. This initial curing step was followed by other dynamic experiment where the decomposition behaviour of such samples was also studied at different heating rates (10- 35 C/min). Thus, four experiments can be obtained by combining two heating rates in each step, resulting in different paths along the time temperature transformation (TTT) diagrams; these diagrams, where different phases in the epoxy system are represented (liquid, gel, rubber, glass, char), are used in bibliography [1,2] to explain the behaviour of epoxy systems at different temperatures and times. Relevant differences in thermal stability of samples were observed in each case, which behaviour can be qualitatively explained on the basis of the position of the mentioned paths in a generalised TTT diagram.

MATERIALS
The DGEBA resin Epikote 828 from Shell and the anhydride, which already includes a BDMA salt as initiator Lindride 36 Y from Lindau Chemicals were used. Resin and anhydride were mixed and used straight in the different experiments described. The stoichometric ratio were determined by measuring the minimum amount of anhydride that yields the maximum glass transition attainable by curing different blends resin-anhydride.
140 120

Glass transition (C)

100 80 60 40 20 0 30 40 50 Anhydride mass fraction (%)

Stoichometric ratio~46%

THERMAL DEGRADATION
THERMAL BEHAVIOUR OF SAMPLES WITH DIFFERENT ANHYDRIDE MASS FRACTION
100 90 80

Weight loss (%)

70 60 50 40 30 20 10 0 100

Epoxy resin Anhydride 46% (stoichometric ratio) 57% 20% 65% 75%

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Temperature (C)

THERMAL BEHAVIOUR OF A STOICHOMETRIC SAMPLE CURED AT DIFFERENT SCANNING RATES

Char zone

POLYMERIZATION KINETICS
Calorimetric curves of mixtures anhydride-resin show a complicated pattern. Depending on the anhydride concentration it is possible to observe different processes. For example, samples containing anhydride concentration above it stoichometric ratio present (samples with 65 % and 75 % of anhydride) one initial exothermic peak corresponding to heteropolymerisation of anhydride and resin and two endothermic peaks at higher temperatures corresponding to evaporation of anhydride and thermal degradation of the polymer formed. On the opposite side, samples containing less anhydride than the amount corresponding to the stoichometric ratio (samples with 10 % and 20 % of anhydride) shows two exothermic peaks, one of them corresponding to heteropolymerisation of resin and anhydride, and other corresponding to homopolymerisation of the resin in excess; in addition a wide endothermic peak is also observed and it is atributted to degradation of homopolymer and heteropolymer formed at lower temperatures.
Heteropolymerisation Homopolymerisation
20% 75%
Heat Flow (arbitrarial units)

120 100
Weight l oss (%)

Sol/Gel glass Liquid

Cured at 10 C/min Cured at 35 C/min

80 60 40 20 0 290

Sol glass
Starting Point Sample stage after the curing step Sample stage when degradation begins

Log time

340

390 Temperature (C)

440

490

65% 10%

Exothermic

REFERENCES
[1] J.Lange, N. Alttmann, C.T. Kelly and P.J. Halley, Polymer, 2000, 41, 5949 [2] L. Nez, F. Fraga, M.R. Nez and M. Villanueva, Polymer, 2001, 42, 3581
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Temperature (C)