Institute for High Pressure Physics RAS, 142190 Troitsk, Moscow Region, Russia.
J Chem Phys. 2012 Aug 28;137(8):084502. doi: 10.1063/1.4746022.
We present the high pressure dielectric spectroscopy (up to 4.2 GPa) and ultrasonic study (up to 1.7 GPa) of liquid and glassy propylene carbonate (PC). Both of the methods provide complementary pictures of the glass transition in PC under pressure. No other relaxation processes except α-relaxation have been found in the studied pressure interval. The propylene carbonate liquid is a glassformer where simple relaxation and the absence of β-relaxation are registered in the record-breaking ranges of pressures and densities. The equation of state of liquid PC was extended up to 1 GPa from ultrasonic measurements of bulk modulus and is in good accordance with the previous equations developed from volumetric data. We measured the bulk and shear moduli and Poisson's ratio of glassy PC up to 1.7 GPa. Many relaxation and elastic properties of PC can be qualitatively described by the soft-sphere or Lennard-Jones model. However, for the quantitative description of entire set of the experimental data, these models are insufficient. Moreover, the Poisson coefficient value for glassy PC indicates a significant contribution of non-central forces to the intermolecular potential. The well-known correlation between Poisson's ratio and fragility index (obtained from dielectric relaxation) is confirmed for PC at ambient pressure, but it is violated with pressure increase. This indicates that different features of the potential energy landscape are responsible for the evolution of dielectric response and elasticity with pressure increase.
我们展示了液体和玻璃态碳酸丙烯酯(PC)的高压介电光谱(高达 4.2 GPa)和超声研究(高达 1.7 GPa)。这两种方法都提供了 PC 在压力下玻璃化转变的互补图像。在所研究的压力范围内,除了 α-松弛外,没有发现其他松弛过程。碳酸丙烯酯液体是一种玻璃形成体,在创纪录的压力和密度范围内,只记录到简单的松弛和不存在 β-松弛。液体 PC 的状态方程是从超声测量的体积模量扩展到 1 GPa 的,并与从体积数据得出的先前方程很好地吻合。我们测量了玻璃态 PC 的体弹性模量和剪切弹性模量以及泊松比,最高可达 1.7 GPa。PC 的许多弛豫和弹性性质可以用软球或 Lennard-Jones 模型定性地描述。然而,对于整个实验数据的定量描述,这些模型是不够的。此外,玻璃态 PC 的泊松系数值表明非中心力对分子间势有显著贡献。在常压下,PC 证实了泊松比与易碎性指数(由介电弛豫获得)之间的良好相关性,但随着压力的增加而被破坏。这表明,势能景观的不同特征负责介电响应和弹性随压力增加的演变。