Niss Kristine, Jakobsen Bo, Olsen Niels Boye
Department of Mathematics and Physics (IMFUFA), Roskilde University, P.O. Box 260, DK-4000 Roskilde, Denmark.
J Chem Phys. 2005 Dec 15;123(23):234510. doi: 10.1063/1.2136886.
The Gemant-DiMarzio-Bishop model, which connects the frequency-dependent shear modulus to the frequency-dependent dielectric constant, is reviewed and a new consistent macroscopic formulation is derived. It is moreover shown that this version of the model can be tested without fitting parameters. The reformulated version of the model is analyzed and experimentally tested. It is demonstrated that the model has several nontrivial qualitative predictions: the existence of an elastic contribution to the high-frequency limit of the dielectric constant, a shift of the shear modulus loss peak frequency to higher frequencies compared with the loss peak frequency of the dielectric constant, a broader alpha peak, and a more pronounced beta peak in the shear modulus when compared with the dielectric constant. It is shown that these predictions generally agree with experimental findings and it is therefore suggested that the Gemant-DiMarzio-Bishop model is correct on a qualitative level. The quantitative agreement between the model and the data is on the other hand moderate to poor. It is discussed if a model-free comparison between the dielectric and shear mechanical relaxations is relevant, and it is concluded that the shear modulus should be compared with the rotational dielectric modulus, 1(epsilon(omega)-n2), which is extracted from the Gemant-DiMarzio-Bishop model, rather than to the dielectric susceptibility or the conventional dielectric modulus M=1epsilon(omega).
回顾了将频率相关的剪切模量与频率相关的介电常数联系起来的杰曼特-迪马尔齐奥-毕晓普模型,并推导了一种新的一致宏观公式。此外,还表明该模型版本无需拟合参数即可进行测试。对该模型的重新公式化版本进行了分析和实验测试。结果表明,该模型有几个重要的定性预测:介电常数高频极限存在弹性贡献;与介电常数的损耗峰频率相比,剪切模量损耗峰频率向更高频率偏移;α峰更宽;与介电常数相比,剪切模量中的β峰更明显。结果表明,这些预测总体上与实验结果一致,因此表明杰曼特-迪马尔齐奥-毕晓普模型在定性层面上是正确的。另一方面,该模型与数据之间的定量一致性中等至较差。讨论了介电弛豫和剪切力学弛豫之间无模型比较是否相关,并得出结论,应将剪切模量与从杰曼特-迪马尔齐奥-毕晓普模型中提取的旋转介电模量1(ε(ω)-n2)进行比较,而不是与介电常数或传统介电模量M = 1/ε(ω)进行比较。