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向列相 E7 在低填充度分子筛中的分子迁移率。

Molecular mobility of nematic E7 confined to molecular sieves with a low filling degree.

机构信息

Departamento de Química, REQUIMTE, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, Caparica 2829-516, Portugal.

出版信息

J Chem Phys. 2010 Jun 14;132(22):224508. doi: 10.1063/1.3432775.

Abstract

The nematic liquid crystalline mixture E7 was confined with similar filling degrees to molecular sieves with constant composition but different pore diameters (from 2.8 to 6.8 nm). Fourier transform infrared analysis proved that the E7 molecules interact via the cyanogroup with the pore walls of the molecular sieves. The molecular dynamics of the system was investigated by broadband dielectric spectroscopy (10(-2)-10(9) Hz) covering a wide temperature range of approximately 200 K from temperatures well above the isotropic-nematic transition down to the glass transition of bulk E7. A variety of relaxation processes is observed including two modes that are located close to the bulk behavior in its temperature dependence. For all confined samples, two relaxation processes, at frequencies lower than the processes observed for the bulk, were detected. At lower temperatures, their relaxation rates have different temperature dependencies whereas at higher temperatures, they seem to collapse into one chart. The temperature dependence of the slowest process (S-process) obeys the Vogel-Fulcher-Tammann law indicating a glassy dynamics of the E7 molecules anchored to the pore surface. The pore size dependence of both the Vogel temperature and fragility revealed a steplike transition around 4 nm pore size, which indicates a transition from a strong to a fragile behavior. The process with a relaxation rate in between the bulklike and the S-process (I-process) shows no dependence on the pore size. The agreement of the I-process with the behavior of a 5CB surface layer adsorbed on nonporous silica leads to the assignment of E7 molecules anchored at the outer surface of the microcrystals of the molecular sieves.

摘要

向列相液晶混合物 E7 在具有相似填充度的情况下被限制在具有恒定组成但不同孔径(从 2.8 到 6.8nm)的分子筛中。傅里叶变换红外分析证明,E7 分子通过氰基基团与分子筛的孔壁相互作用。通过宽带介电谱(10(-2)-10(9)Hz)研究了系统的分子动力学,该谱涵盖了大约 200K 的宽温度范围,从远高于各向同性-向列相转变的温度下降到 bulk E7 的玻璃化转变温度。观察到多种弛豫过程,包括两个模式,它们在温度依赖性上接近体相行为。对于所有受限的样品,都检测到两个弛豫过程,其频率低于体相观察到的过程。在较低的温度下,它们的弛豫率具有不同的温度依赖性,而在较高的温度下,它们似乎合并为一个图表。最慢过程(S 过程)的温度依赖性遵循 Vogel-Fulcher-Tammann 定律,表明固定在孔表面的 E7 分子的玻璃动力学。Vogel 温度和脆性的孔径依赖性都表明在大约 4nm 孔径处存在阶跃式转变,这表明从强行为到脆性行为的转变。具有介于体相和 S 过程(I 过程)之间的弛豫率的过程与孔径无关。I 过程与吸附在非多孔二氧化硅上的 5CB 表面层的行为一致,导致将固定在分子筛微晶外表面的 E7 分子进行分配。

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