Resin Cure Studies

Two techniques, DMTA and dielectric thermal analysis (DETA) (Chapter 12) have been used for the study of resin cure. DSC (Chapter 7) has also been employed. The application of differential photocalorimetry to the measurement of cure rates of photocurable resins is discussed in Chapter 13. 

In resin cure studies the technique characterises the rheological changes in resins before, during, and after cure. Plots of temperature versus permittivity pinpoint the Tg for the resin during cure. Plots of time versus the logarithm of loss factor enable determinations of vitrification of resins during cure to be carried out. 

G and G increase as molecular weight (cure) advances. G eventually exceeds G as the polymer system gains elasticity due to molecular entanglement and network formation. The crossover of the G and G curves has been related to the gel point for these materials. 

Gorbunova and co-workers [35] studied the cure kinetics of a phenol-urethane composition by DMTA and DSC and compared the results obtained by these techniques. Equations were derived to relate the viscosity and the degree of conversion. Time dependence of the conversion was described by a second-order equation in all cases, although the coefficients of this equation are different for DSC and dynamic mechanical measurements. 

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The TMA technique can be used for Tg-value determinations, resin cure studies, penetration experiments or orientation effect determinations. The most important application is thought to be the linear thermal expansion coefficient (l.e.c.) determination of engineering polymers. An example of this application is given in chapter 3.1.2. The results of a polymer shrinkage experiment monitored by TMA are described in chapter 3.1.3. 

Other applications of DMA are discussed in Sections 10.1 (resin cure studies), 12.2 (photopolymers), 13.3 and 13.7 (phase transition studies), and 18.1 (mechanical properties). 

This technique has found the following applications in addition to those discussed in Sections 10.1 (resin cure studies on phenol urethane compositions) [65], 12.2 (photopolymer studies [66-68]), and 13.3 (phase transitions in PE) [66], Chapter 15 (viscoelastic and rheological properties), and Section 16.4 (heat deflection temperatures) epoxy resin-amine system [67], cured acrylate-terminated unsaturated copolymers [68], PE and PP foam [69], ethylene-propylene-diene terpolymers [70], natural rubbers [71, 72], polyester-based clear coat resins [73], polyvinyl esters and unsaturated polyester resins [74], polyimide-clay nanocomposites [75], polyether sulfone-styrene-acrylonitrile, PS-polymethyl methacrylate (PMMA) blends and PS-polytetrafluoroethylene PMMA copolymers [76], cyanate ester resin-carbon fibre composites [77], polycyanate epoxy resins [78], and styrenic copolymers [79]. 

The principle application of differential photocalorimetry is in resin cure studies (Chapters 11 and 13). 

The principal techniques that have been used in resin cure studies are differential scanning calorimetry (DSC Chapter 7), photocalorimetry (Sections 11.3.1 and 11.3.2), dielectric thermal analysis (DETA Section 12.2.1) and dynamic mechanical thermal analysis (DMTA Section 8.3.2). Earlier differential photocalorimetry (DPC) instruments were based on a DSC instrument. However, these were only partially successful in the analysis of photocurable polymers. The failure to develop a completely adequate system has been the result of two factors. The first and most significant is the change in the intensity of the light with time of operation - as much as an 80% reduction in the first 100 hours of operation. The second reason for the limited success was the lack of data analysis software to convert raw data into easy-to-understand results that could be correlated with actual performance. 

During the press operation, which is actually a form of compression mol ding, the resin-treated laminate pHes are heated under pressure and the resins cured. The initial heating phases cause the resin to melt and flow into voids in the reinforcing ply and bond the individual pHes together. The appHed heat simultaneously causes the resin to polymerize and eventually to cross-link or gel. Therefore, resin viscosity reaches a minimum during the press cycle. This is the point at which the curing process becomes dominant over the melt flow process. Dynamic mechanical and dielectric analyses (11) are excellent tools for study of this behavior. 

Novolaks. Novolak resins are typically cured with 5—15% hexa as the cross-linking agent. The reaction mechanism and reactive intermediates have been studied by classical chemical techniques (3,4) and the results showed that as much as 75% of nitrogen is chemically bound. More recent studies of resin cure (42—45) have made use of tga, dta, gc, k, and nmr (15). They confirm that the cure begins with the formation of benzoxazine (12), progresses through a benzyl amine intermediate, and finally forms (hydroxy)diphenyknethanes (DPM). 

Studies of the particle—epoxy interface and particle composition have been helphil in understanding the mbber-particle formation in epoxy resins (306). Based on extensive dynamic mechanical studies of epoxy resin cure, a mechanism was proposed for the development of a heterophase morphology in mbber-modifted epoxy resins (307). Other functionalized mbbers, such as amine-terminated butadiene—acrylonitrile copolymers (308) and -butyl acrylate—acryhc acid copolymers (309), have been used for toughening epoxy resins. 

Barton, J. M. The Application of Differential Scanning Calorimetry (DSC) to the Study of Epoxy Resins Curing Reactions. Vol. 72, pp. 111 — 154. 

Youngquist etal. (1988) found improvements in both resin distribution and IB values when suitable emulsifiers were used in conjunction with waterborne resins, but considered it unlikely that the improvement in performance could be justified on cost grounds. It was postulated that acetylated wood interfered with the polymerization of the resin, so that it was not fully cured. It has also been suggested that acetic acid, which may be released during board pressing, could accelerate resin curing of resol type resins. In a study to determine whether this was so, acetylation of wood was found to slightly reduce... 

Galperin etal. (1995) has reviewed the work undertaken in the Byelorussian Institute of Technology, including work with PF, UF and melamine resins. Apart from resin curing using conventional heating, microwave curing was also studied. 

In Chapter 2 the DSC technique is discussed in terms of instruments, experimental methods, and ways of analysing the kinetic data. Chapter 3 provides a brief summary of epoxy resin curing reactions. Results of studies on the application of DSC to the cure of epoxy resins are reviewed and discussed in Chapter 4. These results are concerned with the use of carboxylic acid anhydrides, primary and secondary amines, dicyanodiamide, and imidazoles as curing agents. 

DSC is increasingly being applied to the study of epoxy resin cure in combination with other analytical methods such as nuclear magnetic resonance and Fourier transform infra-red spectroscopy, chromatographic methods, and dynamic mechanical or dielectric studies. It is probably as part of such combined investigations that DSC can be used most effectively in basic research, and in quality control and assessment. 

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