化学学报 ›› 2011, Vol. 69 ›› Issue (01): 37-45. 上一篇    下一篇

研究论文

基于位形熵模型的山梨醇玻璃焓松弛的量热分析

高才*,陈开松,叶斌,杨锁,刘向农,江斌   

  1. (合肥工业大学机械与汽车工程学院 合肥 230009)
  • 投稿日期:2010-04-18 修回日期:2010-09-02 发布日期:2010-09-12
  • 通讯作者: 高才 E-mail:gao_cai@hotmail.com
  • 基金资助:

    国家自然科学基金项目;安徽省自然科学基金

Calorimetric Study on the Enthalpy Relaxation in Sorbitol Based on the Configurational Entropy Model

GAO Cai, CHEN Kai-Song, YE Bin, YANG Suo, LIU Xiang-Nong, JIANG Bin   

  1. (School of Mechanical and Automotive Engineering, Hefei University of Technology, Hefei 230009)
  • Received:2010-04-18 Revised:2010-09-02 Published:2010-09-12

利用DSC技术考察了无定形山梨醇体系的焓松弛行为, 在10 K•min-1的升温速率下测定了经历不同降温速率(0.5~20 K•min-1)的山梨醇在玻璃化转变(Tg)前后的比热容[cp(T)]. 利用基于位形熵演变的焓松弛现象学模型(GR模型)模拟了实验数据. 不论是否假设松弛过程存在一个亚稳极限态, 模型参数均能很好地重现经历不同热历史体系的升温cp(T)曲线. 在物理意义明确的模型参数组中, 除了非指数参数随降温速率的增加而增加外, 其余均不随热历史的变化而变化. 拟合较低降温速率下cp(T)曲线获得的GR模型参数的预测力明显好于在较大降温速率下获得的结果. 由于松弛时间对拟合过程中选择的“固定参数”的取值很敏感, 因此模型能否预测体系的比热容不能看成确定松弛时间的唯一依据. 在利用GR模型分析无定形山梨醇体系的脆度时, 如果选择极限假想温度作为Tg, 会导致计算结果明显小于文献值.

关键词: 焓松弛, 位形熵, 玻璃化转变, 脆度, 山梨醇, 差示扫描量热法

Enthalpy relaxation dynamics of amorphous D-sorbitol has been studied by differential scanning calorimetry (DSC). A series of specific heat capacity curves (cp(T)) were measured on heating (10 K•min-1) after cooling the sample at different rates ranged between 0.5 and 20 K•min-1. A phenomenological model of enthalpy relaxation based on the evolution of configurational entropy (GR model) was used to simulate the experimental data. All the experimental traces can be fairly well reproduced by this model, no matter whether a metastable limit state of relaxation process is assumed. The physically reasonable model parameters seemed to be independent of thermal history, except the nonexponential parameter, which increased slightly as the cooling rate increasing. The model parameter sets obtained under lower cooling rates show better predictive ability than those obtained under higher ones. Since the calculated relaxation time value is strongly dependent on the “fixed parameter” value, the predictive ability to the cp(T) curves is not the only criterion for the determination of relaxation time. Take the limit fictive temperature as Tg in the fragility calculation leads to an significantly smaller value than the published data.

Key words: enthalpy relaxation, configurational entropy, glass transition, fragility, D-sorbitol, differential scanning calorimetry (DSC)