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对两种接近玻璃化转变温度的一元醇中剪切机械和介电弛豫过程的研究。

Investigation of the shear-mechanical and dielectric relaxation processes in two monoalcohols close to the glass transition.

作者信息

Jakobsen Bo, Maggi Claudio, Christensen Tage, Dyre Jeppe C

机构信息

DNRF Centre Glass and Time, IMFUFA, Department of Sciences, Roskilde University, Postbox 260, DK-4000 Roskilde, Denmark.

出版信息

J Chem Phys. 2008 Nov 14;129(18):184502. doi: 10.1063/1.3007988.

Abstract

Shear-mechanical and dielectric measurements on the two monohydroxy (monoalcohol) molecular glass formers 2-ethyl-1-hexanol and 2-butanol close to the glass-transition temperature are presented. The shear-mechanical data are obtained using the piezoelectric shear-modulus gauge method covering frequencies from 1 mHz to 10 kHz. The shear-mechanical relaxation spectra show two processes, which follow the typical scenario of a structural (alpha) relaxation and an additional (Johari-Goldstein) beta relaxation. The dielectric relaxation spectra are dominated by a Debye-type peak with an additional non-Debye peak visible. This Debye-type relaxation is a common feature peculiar to monoalcohols. The time scale of the non-Debye dielectric relaxation process is shown to correspond to the mechanical structural (alpha) relaxation. Glass-transition temperatures and fragilities are reported based on the mechanical alpha relaxation and the dielectric Debye-type process, showing that the two glass-transition temperatures differ by approximately 10 K and that the fragility based on the Debye-type process is a factor of 2 smaller than the structural fragility. If a mechanical signature of the Debye-type relaxation exists in these liquids, its relaxation strength is at most 1% and 3% of the full relaxation strength of 2-butanol and 2-ethyl-1-hexanol, respectively. These findings support the notion that it is the non-Debye dielectric relaxation process that corresponds to the structural alpha relaxation in the liquid.

摘要

本文展示了在接近玻璃化转变温度时,对两种单羟基(单醇)分子玻璃形成剂2-乙基-1-己醇和2-丁醇进行的剪切力学和介电测量。剪切力学数据是使用压电剪切模量测量法获得的,测量频率范围为1 mHz至10 kHz。剪切力学弛豫谱显示出两个过程,它们遵循结构(α)弛豫和额外的(乔哈里-戈尔茨坦)β弛豫的典型情况。介电弛豫谱以一个德拜型峰为主,还可见一个额外的非德拜峰。这种德拜型弛豫是单醇特有的常见特征。非德拜介电弛豫过程的时间尺度与机械结构(α)弛豫相对应。基于机械α弛豫和介电德拜型过程报告了玻璃化转变温度和脆性,结果表明两个玻璃化转变温度相差约10 K,并且基于德拜型过程的脆性比结构脆性小2倍。如果这些液体中存在德拜型弛豫的力学特征,其弛豫强度分别至多为2-丁醇和2-乙基-1-己醇完全弛豫强度的1%和3%。这些发现支持了这样一种观点,即与液体中的结构α弛豫相对应的是非德拜介电弛豫过程。

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