Drzewicz Anna, Jasiurkowska-Delaporte Małgorzata, Juszyńska-Gałązka Ewa, Zając Wojciech, Kula Przemysław
Institute of Nuclear Physics, Polish Academy of Sciences, PL-31342 Krakow, Poland.
Phys Chem Chem Phys. 2021 Apr 14;23(14):8673-8688. doi: 10.1039/d0cp06203k. Epub 2021 Mar 30.
The relaxation dynamics in the thermodynamic states of the glass-forming antiferroelectric liquid crystal (S)-4'-(1-methyloctyloxycarbonyl) biphenyl-4-yl 4-[7-(2,2,3,3,4,4,4-heptafluorobutoxy) heptyl-1-oxy]-benzoate (3F7HPhH7) was studied by broadband dielectric spectroscopy (BDS). Two glass transitions were found at T = 259 K and T = 239 K, which were associated with the freezing of anti-phase motions and reorientation around the long molecular axis in the antiferroelectric SmC* phase, respectively. The low temperature α2-relaxation process shows a Vogel-Fulcher-Tammann (VFT)-type temperature dependence of its structural relaxation time τ(T). The two secondary β- and γ-relaxation modes ascribed to the intramolecular motions observed in the glassy state show Arrhenius behaviour of τ(T). Analysing the band shifts and the oscillator strengths of specific IR absorption bands and their temperature dependencies enables comparing them with the dielectrically determined relaxation dynamics. The kinetics of the isothermal cold crystallization in the temperature range between T and T was studied in detail using the Avrami and Avrami-Avramow models. This process depends primarily on the diffusion rate and the activation energy is equal to 132 kJ mol. The obtained values of the Avrami exponent n suggest that the crystal growth is three-dimensional.
通过宽带介电谱(BDS)研究了玻璃态反铁电液晶(S)-4'-(1-甲基辛氧基羰基)联苯-4-基 4-[7-(2,2,3,3,4,4,4-七氟丁氧基)庚基-1-氧基]-苯甲酸酯(3F7HPhH7)在热力学状态下的弛豫动力学。在 T = 259 K 和 T = 239 K 处发现了两个玻璃化转变,它们分别与反铁电 SmC* 相中反相运动的冻结以及围绕长分子轴的重取向有关。低温 α2 弛豫过程显示出其结构弛豫时间 τ(T) 的Vogel-Fulcher-Tammann(VFT)型温度依赖性。归因于玻璃态中分子内运动的两个次级 β 和 γ 弛豫模式显示出 τ(T) 的阿累尼乌斯行为。分析特定红外吸收带的频移和振子强度及其温度依赖性,可以将它们与通过介电方法确定的弛豫动力学进行比较。使用 Avrami 模型和 Avrami-Avramow 模型详细研究了在 T 和 T 之间温度范围内的等温冷结晶动力学。这个过程主要取决于扩散速率,活化能等于 132 kJ/mol。得到的 Avrami 指数 n 值表明晶体生长是三维的。