Cangialosi Daniele, Alegría Angel, Colmenero Juan
Facultad de Química, Centro de Física de Materiales Centro Mixto (CSIC-UPV/EHU), Apartado 1072, 20080 San Sebastian, Spain.
J Chem Phys. 2009 Mar 28;130(12):124902. doi: 10.1063/1.3098904.
Using a simple mathematical formalism, we show that temperature dependent nonexponential relaxation found in glass-forming liquids and amorphous polymers, often resulting in a decrease in the stretching exponent when decreasing temperature, can be suitably described assuming the combination of an intrinsic stretched response and the existence of temperature independent heterogeneities. The effect of the latter is incorporated by assuming a Gaussian distribution of Vogel temperatures. Comparison with experimental data of a large number of glass formers showed that this approach is able to quasiquantitatively describes the temperature dependence of the stretching exponent using the width of the distribution as the single fitting parameter. According to this approach, the rapidity of the decrease in the stretching exponent with decreasing temperature depends not only on the magnitude of the standard deviation of Vogel temperatures but also on the value of the intrinsic stretching exponent and on the fragility of the glass former. The latter result is able to rationalize, at least partially, the empirical correlation between the fragility and the stretching exponent at T(g).
使用一种简单的数学形式体系,我们表明,在玻璃形成液体和无定形聚合物中发现的与温度相关的非指数弛豫(通常在温度降低时拉伸指数会减小),可以通过假设固有拉伸响应与与温度无关的不均匀性的存在相结合来得到恰当描述。后者的影响通过假设沃格尔温度的高斯分布来纳入。与大量玻璃形成体的实验数据比较表明,这种方法能够使用分布宽度作为单一拟合参数来准定量地描述拉伸指数的温度依赖性。根据这种方法,拉伸指数随温度降低而减小的速度不仅取决于沃格尔温度标准差的大小,还取决于固有拉伸指数的值以及玻璃形成体的脆性。后一结果至少能够部分地解释在玻璃化转变温度(Tg)下脆性与拉伸指数之间的经验相关性。