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基于动态特性的玻璃形成体中次级弛豫的分类

Classification of secondary relaxation in glass-formers based on dynamic properties.

作者信息

Ngai K L, Paluch M

机构信息

Naval Research Laboratory, Washington, DC 20375-5320, USA.

出版信息

J Chem Phys. 2004 Jan 8;120(2):857-73. doi: 10.1063/1.1630295.

Abstract

Dynamic properties, derived from dielectric relaxation spectra of glass-formers at variable temperature and pressure, are used to characterize and classify any resolved or unresolved secondary relaxation based on their different behaviors. The dynamic properties of the secondary relaxation used include: (1) the pressure and temperature dependences; (2) the separation between its relaxation time taubeta and the primary relaxation time taualpha at any chosen taualpha; (3) whether taubeta is approximately equal to the independent (primitive) relaxation time tau0 of the coupling model; (4) whether both taubeta and tau0 have the same pressure and temperature dependences; (5) whether it is responsible for the "excess wing" of the primary relaxation observed in some glass-formers; (6) how the excess wing changes on aging, blending with another miscible glass-former, or increasing the molecular weight of the glass-former; (7) the change of temperature dependence of its dielectric strength Deltaepsilonbeta and taubeta across the glass transition temperature Tg; (8) the changes of Deltaepsilonbeta and taubeta with aging below Tg; (9) whether it arises in a glass-former composed of totally rigid molecules without any internal degree of freedom; (10) whether only a part of the molecule is involved; and (11) whether it tends to merge with the alpha-relaxation at temperatures above Tg. After the secondary relaxations in many glass-formers have been characterized and classified, we identify the class of secondary relaxations that bears a strong connection or correlation to the primary relaxation in all the dynamic properties. Secondary relaxations found in rigid molecular glass-formers belong to this class. The secondary relaxations in this class play the important role as a precursor or local step of the primary relaxation, and we propose that only they should be called the Johari-Goldstein beta-relaxation.

摘要

动态性质源自玻璃形成体在可变温度和压力下的介电弛豫谱,基于其不同行为用于表征和分类任何已分辨或未分辨的二级弛豫。所使用的二级弛豫的动态性质包括:(1)压力和温度依赖性;(2)在任何选定的τα下其弛豫时间τβ与主弛豫时间τα之间的间隔;(3)τβ是否近似等于耦合模型的独立(原始)弛豫时间τ0;(4)τβ和τ0是否具有相同的压力和温度依赖性;(5)它是否对某些玻璃形成体中观察到的主弛豫的“过剩翼”负责;(6)过剩翼在老化、与另一种可混溶玻璃形成体混合或增加玻璃形成体分子量时如何变化;(7)其介电强度Δεβ和τβ的温度依赖性在玻璃化转变温度Tg处的变化;(8)在Tg以下老化时Δεβ和τβ的变化;(9)它是否出现在由完全刚性分子组成且没有任何内部自由度的玻璃形成体中;(10)是否仅涉及分子的一部分;以及(11)在高于Tg的温度下它是否倾向于与α弛豫合并。在对许多玻璃形成体中的二级弛豫进行表征和分类之后,我们确定在所有动态性质中与主弛豫有强联系或相关性的二级弛豫类别。在刚性分子玻璃形成体中发现的二级弛豫属于此类。此类中的二级弛豫作为主弛豫的前驱或局部步骤发挥重要作用,并且我们提出只有它们才应被称为乔哈里 - 戈尔茨坦β弛豫。

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