No / The cure of polydicyclopentadiene conducted by ring-opening metathesis polymerisation in the presence of a Grubbs catalyst was studied using non-invasive Raman spectroscopy. The spectra of the monomer precursor and polymerised product were fully characterised and all stages of polymerisation monitored. Because of the monomer's high reactivity, the cure process is adaptable to reaction injection moulding and reactive rotational moulding. The viscosity of the dicyclopentadiene undergoes a rapid change at the beginning of the polymerisation process and it is critical that the induction time of the viscosity increase is determined and controlled for successful manufacturing. The results from this work show non-invasive Raman spectroscopic monitoring to be an effective method for monitoring the degree of cure, paving the way for possible implementation of the technique as a method of real-time analysis for control and optimisation during reactive processing. Agreement is shown between Raman measurements and ultrasonic time of flight data acquired during the initial induction period of the curing process.

The interpretation and modelling of the dielectric response of thermosetting materials during cure was the main focus of this study. The equivalence of complex permittivity and complex impedance in terms of information content was outlined in a series of case studies covering the separate effects of dipolar movements and charge migration as well as the combined effect of the two polarisation mechanisms. Equivalent electrical circuits were used in order to model the evolution of the complex impedance during cure. A numerical method that can model consecutive spectra throughout the cure was developed. The method is based on Genetic Algorithms and requires only input from the modelling of the initial spectra. Complex impedance spectra were collected during the cure of a commercial epoxy resin formulation under isothermal and dynamic heating conditions. The spectra were analysed and modelled. The modelling was successful over the whole frequency range of the measurements (1 Hz – 1 MHz). The analysis of the estimated model parameters showed that charge migration dominates the dielectric response in a wide frequency range. In addition, the modelling algorithm also distinguished between the effects of electrode polarisation and dipolar movements in the signal. A new equivalent circuit was used in order to map the frequency regions where the each one of the three phenomena that together comprise the dielectric signal can be monitored most effectively. A chemical cure kinetics model was developed for the studied system. A correlation between the maximum point of the imaginary impedance spectrum and the reaction conversion was established. A mathematical model, based on a simple linear dependence of the dielectric signal on conversion and temperature, was built. The model predictions agreed well with the experimental data. The aim of simplifying the interpretation of the dielectric signals led to the development of a new experimental technique. Temperature Modulated Dielectric Analysis employs temperature modulations superimposed on an underlying thermal profile in order to separate the influence on the signal of the temperature alone from that of the cure reaction. The early study carried out here shows that such measurements are feasible and reveals important issues for its further development.

Our motivation for this work is based on the need to monitor the cure and inservice health of composite materials. We describe the continuation of an effort to design a multi-functional fiber optic sensor which can be embedded in polymeric composite laminates for monitoring the degree of cure during its fabrication, as well as internal composite strains occurring post-cure.3 In short, this dual-purpose sensor combines the characteristics of a Fresnel reflectometer with those of the extrinsic Fabry-Perot interferometer. For monitoring cure, a broadband source is used so the output intensity of the sensor is amplitude-modulated as the refractive index of the composite is increased during the polymerization process. Post-cure, a coherent light source is implemented so a. sinusoidal variation of the output signal occurs when strains within the composite cause the sensor output to be phase-modulated. We demonstrate the measurement of refractive index with the Fresnel reflectometer/EFPL and test it as an embedded refractive index monitor. Our experimental results demonstrate that the refractive index of 5-minute epoxy increases by approximately 2 % during the cure process. In addition, the sensor can be used as an interferometer to measure internal composite strains, where the phase difference between consecutive fringe peaks is one-half the wavelength of the source. / Master of Science