Kaminski K, Adrjanowicz K, Kaminska E, Paluch M
Institute of Physics, Silesian University, Katowice, Poland.
Phys Rev E Stat Nonlin Soft Matter Phys. 2011 Jun;83(6 Pt 1):061502. doi: 10.1103/PhysRevE.83.061502. Epub 2011 Jun 13.
Time-dependent isothermal dielectric measurements were carried out deeply in the glassy state on two very important saccharides: sucrose and trehalose. In both compounds two prominent secondary relaxation processes were identified. The faster one is an inherent feature of the whole family of carbohydrates. The slower one can also be detected in oligo- and polysaccharides. It was shown earlier that the β process is the Johari-Goldstein (JG) relaxation coupled to motions of the glycosidic linkage, while the γ relaxation originates from motions of the exocyclic hydroxymethyl unit. Recently, it was shown that the JG relaxation process can be used to determine structural relaxation times in the glassy state [R. Casalini and C. M. Roland, Phys. Rev. Lett. 102, 035701 (2009)]. In this paper we present the results of an analysis of the data obtained during aging using two independent approaches. The first was proposed by Casalini and Roland, and the second one is based on the variation of the dielectric strength of the secondary relaxation process during aging [J. K. Vij and G. Power, J. Non-Cryst. Solids 357, 783 (2011)]. Surprisingly, we found that the estimated structural relaxation times in the glassy state of both saccharides are almost the same, independent of the type of secondary mode. This finding calls into question the common view that secondary modes of intramolecular origin do not provide information about the dynamics of the glassy state.
在玻璃态下对两种非常重要的糖类物质——蔗糖和海藻糖进行了与时间相关的等温介电测量。在这两种化合物中,都识别出了两个显著的二级弛豫过程。较快的那个是整个碳水化合物家族的固有特征。较慢的那个在寡糖和多糖中也能检测到。早些时候已经表明,β过程是与糖苷键运动相关的乔哈里 - 戈尔茨坦(JG)弛豫,而γ弛豫源于环外羟甲基单元的运动。最近,有人表明JG弛豫过程可用于确定玻璃态下的结构弛豫时间[R. 卡萨利尼和C. M. 罗兰,《物理评论快报》102, 035701 (2009)]。在本文中,我们展示了使用两种独立方法对老化过程中获得的数据进行分析的结果。第一种方法是由卡萨利尼和罗兰提出的,第二种方法基于老化过程中二级弛豫过程的介电强度变化[J. K. 维杰和G. 鲍尔,《非晶态固体杂志》357, 783 (2011)]。令人惊讶的是,我们发现两种糖类物质在玻璃态下估计的结构弛豫时间几乎相同,与二级模式的类型无关。这一发现对分子内起源的二级模式不能提供有关玻璃态动力学信息的普遍观点提出了质疑。