Glass transition phenomena in two-component plastic crystals: study of hexasubstituted benzenes

We have critically examined the relaxation that is known to occur in the crystalline phase of pentachloronitrobenzene (PCNB) and 2,3,4,5,6-pentabromotoluene using dielectric spectroscopy and differential scanning calorimetry (DSC). Within the resolution of our experimental setup, a relaxation process similar to that of the primary (or alpha-) relaxation is found. A slight deviation from Arrhenius behavior is noticed only in the vicinity of the glass transition temperature (T(g)). This deviation and a small steplike change found in the DSC scans at T(g) indicates that the "fragility" of these plastic crystals is rather low. However, in PCNB, the dielectric strength (Deltaepsilon) of the above said alpha-process did not change appreciably with temperature, and, interestingly, a small addition of an impurity such as pentachlorobenzene (PCB) to the molten state of PCNB drastically lowered the dielectric strength and the calorimetric signature of glass transition phenomena in the DSC data at T(g). The room-temperature powder X-ray diffraction measurements in combination with the DSC data in the melting temperature region did not indicate any observable change in the crystalline structure. A residual alpha-process with no significant change in the shape of the dielectric spectrum indicates that the hindrance to the rotational motion of PCNB molecules is caused by the presence of a small number of PCB molecules in the crystalline lattice of PCNB over a certain region. Outside of this region, the original PCNB disordered phase is preserved, which is the origin of the residual alpha-process. With a further increase in PCB concentration, the alpha-process, characteristic of pure PCNB, vanishes, and instead another relaxation develops. This process is explained with the help of a solid-liquid phase diagram of the alpha-process of the plastic phase of 2:1 and 1:2 compound formations, which are stable below 386 +/- 1 and 366 +/- 1 K, respectively.