Carpentier L, Decressain R, Descamps M
Laboratoire de Dynamique et Structure des Matériaux Moléculaires, UMR CNRS 8024, Bat. P5, Université de Lille, 59655 Villeneuve d'Ascq, France.
J Chem Phys. 2008 Jan 14;128(2):024702. doi: 10.1063/1.2813436.
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.
在[170 - 250 K]温度范围内,在等温等时条件下对氰基金刚烷的过冷塑料晶体相进行了介电测量,每次实验使用新样品。在等温过程中进行的测量使我们能够强调接近玻璃化转变温度的转变效应,这种转变导致化合物动态行为发生变化。介电弛豫时间的温度依赖性在整个亚稳区域呈现出阿仑尼乌斯演化,并且在量热玻璃化转变温度下给出的值为1 s,即比通常的值[τ(T(g))≈100 s]低两个数量级。这些结果表明,用其他技术观察到的Vogel - Fulcher - Tammann行为在布里渊区中心(q = 0)并未出现,并且这种玻璃形成体的玻璃化转变并非与单个分子偶极子的翻转运动冻结相关,而是与反铁电局部有序的涨落冻结有关。