Relaxation dynamics of orientationally disordered plastic crystals: effect of dopants

We have examined the relaxation that occurs in the supercooled plastic crystalline phases of pentachloronitrobenzene (PCNB), dichlorotetramethylbenzene (DCTMB), trichlorotrimethylbenzene (TCTMB) along with some of their deuterated samples, and 1-cyanoadamantane (CNADM) in the presence of intentionally added dopants. The experimental techniques used in the present study are dielectric spectroscopy and differential scanning calorimetry (DSC). Only one relaxation process similar to that of the primary (or alpha-) relaxation characteristic of glass-forming materials is found, but there is no indication of any observable secondary relaxation within the resolution of our experimental setup. The alpha-process can reasonably be described by a Havriliak-Negami (HN) shape function throughout the frequency range. However, in the case of PCNB the dielectric strength (Delta epsilon) of the above said alpha-process does not change appreciably with temperature, though interestingly, a small addition of a dopant such as pentachlorobenzene (PCB), trichlorobenzene (TCB), and chloroadamantane (CLADM) to the molten state of PCNB drastically lowers the dielectric strength by a factor of 4 to 8. Powder X-ray diffraction measurements at room temperature and DSC data do not indicate any appreciable change in the crystalline structure. It is noticed that the effect of PCB as a dopant on the magnitude of alpha-process of CNADM is moderate, whereas both PCB and TCB as dopants show a much reduced effect on the relaxation in DCTMB and TCTMB. It is suggested that the drastic changes in the dielectric strength of the alpha-process is due to the rotational hindrance caused by the presence of a small number of dopant molecules in the host crystalline lattice. In the above context, the possibility of a certain degree of antiparallel ordering of dipoles is also discussed.