Influence of phase transformation on the low temperature dielectric measurements in 1-cyanoadamantane.

Dielectric measurements have been performed on the supercooled plastic crystal phase of cyanoadamantane under isothermal and isochronal conditions in the temperature range [170-250 K], each experiment with a new sample. The measurements performed in the course of isotherms allowed us to emphasize the effects of the transformations close to the glass transition temperature leading to a change in the dynamic behavior of the compound. The temperature dependence of the dielectric relaxation times exhibits an Arrhenius evolution on the whole metastable domain and gives at the calorimetric glass transition temperature a value of 1 s, i.e., two orders of magnitude lower than the usual value [tau(T(g)) congruent with 100 s]. These results indicate that the Vogel-Fulcher-Tammann behavior observed with other techniques does not appear in the Brillouin zone center (q=0) and that the glass transition for this glass former is not associated with the freezing out of the tumbling motion of individual molecular dipoles but to the freezing out of fluctuations of an antiferroelectric local ordering.

Molecular mobility in glass forming fananserine: a dielectric, NMR, and TMDSC investigation.

PURPOSE: This study was conducted to characterize the molecular mobility of supercooled fananserine and derive from this analysis the non-Arrhenius and nonexponential properties of the primary alpha-relaxation. METHODS: The use of three investigation techniques of the molecular mobility, namely, dielectric relaxation, modulated differential scanning calorimetry, and proton nuclear magnetic resonance, allowed us to describe the dynamic properties of supercooled fananserine on a wide range of frequencies and temperatures, ranging from the melting temperature T(m) = 372 K down to the glass transition temperature T(g) = 292 K. RESULTS: We emphasized the capacity of these three techniques to give a coherent set of information. We used the coupling-model theory to interpret the dielectric results. It allowed us to identify two relaxation processes (alpha and beta), corresponding to different molecular motions. The temperature evolution of the alpha-relaxation indicates that fananserine is a fragile glass former, as reflected by the steepness index value, m = 77. The temperature T(o) where the relaxation times diverge was also determined. CONCLUSIONS: The description of the dielectric relaxation data in terms of the Kohlrausch-Williams-Watt relaxation function has shown the existence of an additional low-amplitude relaxation process assigned to the so-called Johari-Goldstein process. Mainly concerned by the primary alpha-process directly involved in the glass formation, we derived from this analysis the characteristic features of this process and showed that supercooled fananserine is characterized by a strongly non-Arrhenius and nonexponential behavior.

Dynamics of the amorphous and crystalline alpha-, gamma-phases of indomethacin.

Crystallization processes in indomethacin can be observed below Tg leading to different forms depending on the thermal treatment: a rapid and deep quench below Tg leads to the metastable alpha-phase and a slow cooling close to Tg gives rise to the stable gamma-phase. To understand this atypical behavior, we have studied the molecular mobility of the amorphous and crystalline forms of indomethacin by dielectric relaxation and 1H NMR spectroscopy. Two relaxations were detected in the glassy state obtained from the deeply quenched liquid. One, also present in the gamma-phase, was attributed to local rotations. The other one, of very low amplitude, was attributed to the Johari-Goldstein relaxation. The results allowed to discuss the relationship between these two relaxation processes and the crystallization properties of amorphous indomethacin.

Onset of slow dynamics in difluorotetrachloroethane glassy crystal.

Complementary neutron spin-echo and x-ray experiments and molecular-dynamics simulations have been performed on difluorotetrachloroethane (CFCl2-CFCl2) glassy crystal. Static, single-molecule reorientational dynamics and collective dynamics properties are investigated. Our results confirm the strong analogy between molecular liquids and plastic crystals. The orientational disorder is characterized at different temperatures and a change in the nature of rotational dynamics is observed. A careful check of the rotational diffusion model is performed using self-angular correlation functions Cl with high l values and compared to results obtained on molecular liquids composed of A-B dumbbells. Below the crossover temperature at which slow dynamics emerge, we show that some scaling predictions of the mode coupling theory hold and that alpha-relaxation times and nonergodicity parameters are controlled by the nontrivial static correlations.

Nuclear magnetic resonance and dielectric investigations of molecular motions in a glassy crystal: the mixed compound (CN-adm)0.75(Cl-adm)0.25.

The dynamic properties of plastic crystalline mixed adamantane's derivatives namely cyanoadamantane (75%) and chloroadamantane (25%) were investigated by dielectric and nuclear magnetic resonance (NMR) spectroscopy, covering a spectral range of 12 decades in the temperature range 110-420 K. Phase transformations were studied and dynamical parameters of the plastic (I), glassy (Ig), and ordered (III) phases were determined and compared with those of pure compounds. The dynamics of the supercooled plastic phase is characterized by an alpha-process exhibiting an Arrhenius behavior which classified the mixed compound as a strong glass former. In the plastic phase, NMR relaxation times were interpreted by using a Frenkel model, which takes into account structural equilibrium positions. This model explains adequately the experimental results by considering two molecular motions. In both the glassy state and plastic phase the motional parameters agree with those of 1-cyanoadamantane. On the contrary, in the ordered phase, the motional parameters related to the uniaxial rotation of chloroadamantane molecules indicate an accelerated motion.

Relaxation modes in glass forming meta-toluidine.

The dynamics in supercooled meta-toluidine was studied using dielectric relaxation, modulated differential scanning calorimetry, proton spin-lattice relaxation times, and viscosity measurements. The combination of these different techniques has clearly shown a large decoupling of the relaxation modes whose origin is attributed to the formation of clusters via the NH2 bonding. This decoupling starts at a temperature also corresponding to a change of the dynamical behavior from a high temperature Arrhenius evolution to a Vogel-Fulcher-Tamman low temperature evolution.

Nuclear magnetic resonance of confined MBBA.

Confinement of liquid crystals in small pores changes their thermodynamic, structural, and dynamical properties. In this study we are concerned with solid, liquid crystalline, and isotropic liquid phase behaviour of the nematogenic compound MBBA confined in small pores of variable diameters. Controlled Pores Glasses (CPG) were used, the morphology of these materials is a three-dimensional connected network of cylindrical pores. The present data investigates the dynamic behaviour of MBBA in porous media over the temperature range from 130 K to 330 K as a function of pores diameters.