Chlorine loss and mass loss from polyvinylchloride and polyvinylidenchloride under the electron beam

The loss of chlorine during the irradiation of PVC and PVDC in the electron microscope has been measured by the decay of the X-ray chlorine Kα signal. A number of factors affecting the measured beam damage curves have been considered and the experimental errors reduced to +- 10%. The results show that the chlorine decay curves can be best described by the sum of two exponentials, corresponding to the two different chlorine decay processes, these being: the dehydrochlorination of the polymer molecules and the dehydrochlorination of the polyene structure formed by the beam damage. The higher initial chlorine content of PVDC compared to PVC will result in a larger amount of chlorine atoms reacting with the polyene structure, which is more stable in the electron beam than the undamaged polymer. The chlorine loss, measured by X-ray analysis, has been compared to the mass loss, measured by energy loss analysis, and also with the volume changes of isolated spherical PVC particles. It has been concluded that the mass loss is almost entirely due to chlorine loss and that the residual structure has a density similar to the undamaged PVC. (author)