丙三醇浓溶液玻璃化转变与结构松弛参数DSC分析  

Glass Transition and Structure Relaxation Parameters of Glycerol/Water Mixtures with High Concentrations: A DSC Study

作　　者：高才[1] 周国燕[1] 胥义[1] 胡桐记[1] 华泽钊[1] 

机构地区：[1]上海理工大学低温医学与食品冷冻研究所,上海200093

出　　处：《Chinese Journal of Chemical Physics》2005年第3期457-462,共6页化学物理学报（英文）

基　　金：ProjectsupportedbytheNationalNaturalScienceFoundationofChina(50376040;50206013);KeySpecialtyFoundationofShanghaiMunicipalEducationCommission;YoungFoundationofShanghaiMunicipalEducationCommission(02GQ25).

摘　　要：利用差示扫描量热仪研究了5种高浓度丙三醇水溶液(60%、70%、80%、90%、100%)的玻璃化转变行为,以考察水分含量和升降温速率对其玻璃化转变行为和结构松弛参数的影响.采用4种线性升降温速率(10、15、20、25K/min)获得玻璃化转变的相关参数.利用GordonTaylor方程对玻璃化转变温度的分析结果表明,水对丙三醇增塑常数的计算结果与升降温速率和玻璃化转变温度的读取方法有很大关系.玻璃化转变过程的比热容变化不仅随水分含量的增加而增加,而且与升降温速率也有一定的依赖关系.结构松弛活化能的计算结果表明,随体系水分含量的增加,体系的结构松弛活化能和动力学脆度都逐渐降低.随水分含量的变化,热力学脆度和动力学脆度表现出相反的变化趋势.In order to examine the effects of water contents and heating/cooling rates on the glass transition and the structure relaxation parameters of glycerol/water mixtures, five aqueous solutions (60%, 70%, 80%, 90% and 100%) were investigated using the differential scanning calorimetry. Four scanning rates (10, 15, 20, 25 K/min) were used to obtain the glass transition parameters. The fitting results of plasticization constants indicated that Gordon-Taylor relationship could not be used effectively without considering scanning rates and that point on calorimetric step was chosen as the glass transition temperature. The specific heat changes during glass transition processes were relative not only to water content but also to heating rates. With the increasing of water contents in glycerol aqueous solutions, the structure relaxation activation energies and dynamic fragilities were decreased. Since the thermodynamic fragilities were increased with the increasing of water content, so the dynamic fragility and thermodynamic fragility were changed inversely if the water contents were changed in glycerol/water mixtures.

关 键 词：玻璃化转变 丙三醇 差示扫描量热法 增塑常数 热容 松弛活化能 脆度 

分 类 号：O645[理学—物理化学]