GLASS-TRANSITION TEMPERATURES FOR SIMPLE MOLECULAR LIQUIDS AND THEIR BINARY-SOLUTIONS
GLASS-TRANSITION TEMPERATURES FOR SIMPLE MOLECULAR LIQUIDS AND THEIR BINARY-SOLUTIONS
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DOI：
10.1021/j100513a016
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发表时间：
1978-01-01
影响因子：
--
通讯作者：
SARE, EJ
中科院分区：
文献类型：
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作者：
ANGELL, CA;SARE, JM;SARE, EJ
在55个二元分子液体系统中，以20 mol%的间隔测量了玻璃化转变温度，并将结果用作（a）通过外推法估计许多在纯态下不玻璃化的常见有机液体的玻璃化转变温度的基础，从而（B）识别共同决定其Tg大小的分子的各种结构特征。在大多数情况下，观察到简单的线性组成依赖性的Tg。讨论了dTJdx的热力学意义。在环己醇的情况下，液体的Tg估计值超过塑性晶体相的已知值10 ℃左右。CC14和CHC13的Tg估计值大大超过了这些物质的气相沉积非晶相的Tg值。近年来，在溶液研究中，越来越多地使用不能结晶并因此在冷却时连续固化（即玻璃化）的溶剂。这在辐射化学中尤其明显，其中玻璃态基质用于捕获辐射分解产物，用于随后的EPR或可见光谱检查，并在随后的Tg退火时研究复合动力学。1在低温电化学研究2，3以及结构和介电弛豫过程的研究中，也对非结晶溶剂感兴趣。4'6在这些研究中，显然希望有一系列具有不同退火点和化学性质的溶剂，以及一些预测退火温度的方法。
Glass transition temperatures have been measured at 20 mol% intervals in 55 binary molecular liquid systems and the results used as a basis for (a) estimating by extrapolations the glass transition temperatures of many common organic liquids which do not vitrify in the pure state and thereby (b) identifying the various structural features of a molecule which collectively determine the magnitude of its Tg. In most cases, simple linear composition dependences are observed for Tg. The thermodynamic significance of dTJdx is discussed. In the case of cyclohexanol Tg estimated for the liquid exceeds the known value of “TJ for the plastic crystal phase by some 10 C. The Tg estimated for CC14 and CHC13 exceed by large intervals the Tg values reported for vapor-depositedamorphous phases of these substances.In recent years there has been increasing utilization, in solutions research, of solvents which fail to crystallize and consequently solidify continuously on cooling (ie, which vitrify). This has been particularly marked in radiation chemistry where the glassy matrix is utilized to trap ra-diolysis products for subsequent EPR or visible spec-troscopic examination and, on subsequent annealing at Tg, to study recombination kinetics. 1 There has also been interest in noncrystallizing solvents in low temperature electrochemical studies2, 3 and in the investigation of structural and dielectric relaxation processes. 4'6 In such studies it is obviously desirable to have available a range of solvents with different annealing points and chemical properties and also some means of predicting the