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Shiro Matsuoka 《Journal of research of the National Institute of Standards and Technology》1997,102(2):213-228
The high frequency end of the relaxation spectrum for polymer molecules involves the rotation of the segmental bonds. This fast relaxation process, however, cannot take place easily in the condensed state crowded by the densely packed conformers, necessitating the slower cooperatively synchronous relaxation. As the temperature is lowered, the domain of cooperativity grows towards the infinite size at the Kauzmann zero entropy temperature, though actually the system deviates from the equilibrium as the glass transition intervenes typically at 50 K above that temperature. The excess enthalpy and entropy drop faster than predicted by the rotational isomeric states which would reach zero only at 0 K. The real ΔCP is greater than that of the RIS value. The actual volume in excess of the crystalline lattice volume, however, points towards zero at 0 K. Thus, a polymer with higher Tg typically exhibits a lower density and modulus in the glassy state. Since the configurational entropy associated with the free volume is proportional to the logarithm of the latter, the Kauzmann temperature can be scaled by ln M, where M is the algebraic average of the conformer molecular weight. The temperature dependence of the most dominant, i.e., the largest equilibrium domain size will result in the Adam-Gibbs and Vogel equations for the characteristic relaxation time. The cooperative domain distribution leads to the relaxation spectrum that follows a power law. The relationship between the characteristic relaxation time and the rate of physical aging is derived. 相似文献
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本文推荐陈林根编著的《工程化学》对化学热力学基本公式△G=△H-T△S的引出方法,试探基础教学的改革。 相似文献
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利用独立分量分析法去除地震噪声 总被引:2,自引:0,他引:2
独立分量分析(ICA)作为盲源分离(BSS)的一种新方法,是分解观测数据中独立信息的有力工具。以往的ICA算法一般假设噪声可以忽略不计,而实际的观测数据中又常常包含一些加性噪声。对于加性噪声的影响不能忽略的情况下,改进的ICA算法首先利用非零时间滞后协方差,应用两步特征值分解法(EVD)可成功地去除部分加性噪声的影响;再利用ICA算法就能更好地分离出原信号。本文通过对地震理论模型和实际资料的试验,说明改进的ICA算法能够有效地克服加性噪声对常规ICA算法的影响,能够分离出地震资料中的有效信号,从而实现利用独立分量分析压制地震资料噪声的目的。 相似文献
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Shannon’s entropy plays an important role in the context of information theory. Since this entropy is not applicable to a system which has survived for some units of time, the concept of residual entropy has been developed in the literature. Here we generalize the residual entropy by choosing a convex function ? with ?(1) = 0. In this paper, some orderings and aging properties have been defined in terms of the generalized residual entropy function and their properties have been studied. Quite a few results available in the literature have been generalized and some distributions (viz. uniform, exponential, Pareto, power series, finite range) have been characterized through the generalized residual entropy. 相似文献
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介绍了集团变分法的集团概率变量、配置熵等统计分析的理论基础及Helmholtz自由能的描述模型.提出了巨势及相对化学势的几何分析理论.讨论了应用集团变分法和巨势分析理论进行相平衡计算的过程,并分析了同结构平衡相图计算的若干实例. 相似文献
18.
Sipra Mahapatra Turaga P. Prasad 《Journal of chemical technology and biotechnology (Oxford, Oxfordshire : 1986)》1992,53(2):201-203
Hydrolysis of Fe(OH)SO4 was carried out in the presence of metallic iron in order to prevent the formation of iron(III) oxides with strongly bonded sulphate. Under the conditions of the experiment, the products were found to be mixtures of ?-Fe2O3 and α-FeOOH. The occluded sulphate, if any, could be easily washed out with water. The hydrolysis reaction passes through an equilibrium state before coming to completion. The entropy with enthalpy of the hydrolysis corresponding to the equilibrium state were found to be 4 e.u. and 0·5 kJ/mol, respectively. The activation energy of the hydrolysis reaction was found to be 21 kJ/mol. 相似文献
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We present a method that is useful in the estimate and assessment of heat capacity data. The approach is based on an analysis of the logarithmic average of the phonon frequencies. In this quantity, that may be easily derived from experimental data on the vibrational entropy, the influence of atomic masses can be exactly accounted for even in polyatomic solids. Our method is applied to Li2O, Na2O, K2O, Rb2O, and Cs2O. In particular, literature data for K2O are critically examined. 相似文献
20.
对投电容器扰动识别和定位的方法进行了改进。针对其他此类方法的不足,比如在电压幅值低时投电容器扰动的识别、定位“可信度不高”等,文中通过提取小波变换的特定层的系数,对需要识别的电容器扰动的分解信号相对增强,而其他扰动的分解信号相对减弱,然后再提取熵特征值,结果表明它可以作为识别低电压时投电容器扰动的依据。在对电容器扰动进行定位时,参考了功率和能量定位法,并对其进行了改进。仿真分析证明,在电压幅值较低时,可以准确和可靠地对电容器扰动进行识别和定位。 相似文献