Entropy,Free Volume,and Cooperative Relaxation

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 ΔC_P 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 T_g 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.     

我国低松弛预应力钢丝钢绞线发展现状和展望

对我国低松弛预应力钢丝、钢绞线的发展及市场现状进行了综述，并对目前我国开发、生产与市场销售的严峻形势作了分析，提醒要上这一项目的厂家要慎重对待。     

聚醚酰亚胺热焓松弛的分子量依赖关系

采用ＤＳＣ对不同分子量的聚醚酰亚胺的等温及动态热焓松弛行为进行了研究，并以ＫＷＷ方程对实验数据进行了非线性拟合。结果表明，分子量对热焓松弛的影响是由高分子端基引起自由体积的差异所致。不同分子量的聚醚酰亚胺分子具有不同数量的端基，淬冷时端基数目的差异将产生不同数量的过剩自由体积，从而影响松弛热焓及松弛速率、低分子量的聚醚酰亚胺松弛相对较快，且起始热焓高，松弛的表观活化能亦较小。     

关于Gibbs函数变关系式引出的探讨

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。     

Power Dissipation in Spintronic Devices Out of Thermodynamic Equilibrium

Quantum limits of power dissipation in spintronic computing are estimated. A computing element composed of a single electron in a quantum dot is considered. Dynamics of its spin due to external magnetic field and interaction with adjacent dots are described via the Bloch equations. Spin relaxation due to magnetic noise from various sources is described as coupling to a reservoir. Resulting dissipation of energy is calculated and is shown to be much less than the thermal limit, ∼kT per bit, if the rate of spin relaxation is much slower than the switching rate. Clues on how to engineer an energy efficient spintronic device are provided.     

低温聚合物结构松弛的数值研究

为了获得低温聚合物的参数和升降温速率对连续升降温无量纲比热容的影响,应用差示扫描量热法(DSC)和TNM的结构松弛模型作出简单的数值研究.结果表明,变换不同比率的升降温速率及不同参数值得到的DSC曲线图形变化能够对聚合物的结构松弛研究有一点参考作用.     

汽轮机回热系统给水焓升的最优分配

从汽轮机回热系统的实际情况出发，运用非线性规划理论和计算机技术，解决了给水焓升设计中的最优分配问题。结合具体实例，针对国产200MW汽轮机回热系统给水焓升的分配进行了说明。     

Changes in polymer foils used in food packaging tested by using differential scanning calorimetry

This work is an experimental study of the differential scanning calorimetry characterisation of polymer materials used in food packaging materials, such as polypropylene (0.03 mm), polyethylene (0.1 and 0.03 mm), poly(D-(-)-Β-hydroxybutyrate) (powder), two-layered polypropylene (0.064 mm), and two-layered polypropylene with poly-vinylidene-chloride (0.012/0.021). The polymer stability was checked by simulation of conditions during food preparation in microwave ovens, sterilisation or rapid freezing. The materials were tested in the temperature range from 40 to 200‡C at different scan rates from 2 to 30°C min⁻¹ during heating or cooling. The enthalpies show a high correlation coefficient (0.964) with scan rate. All samples undergo phase change in the temperature range from 107 to 173°C during heating and enthalpies are in the range from 31.8 to 71.1Jg⁻¹. Upon subsequent cooling from 200°C, the temperature range of phase changes is shifted to lower temperatures from 86 to 102°C with enthalpies ranging from 30.4 to 57.8 J g⁻¹. Experiments with exposure of polymers to microwave radiation and freezing prove that the phase change considering the temperature range is very similar in all experiments.     

Creep of PVDF monofilament sutures: service performance prediction from short-term tests

Isothermal short-term creep of poly (vinylidene fluoride) (PVDF) monofilament sutures was determined at several temperatures between 10 and 90 °C under the stress of 10 MPa. Long term service performance was predicted for 10 decades of time. The compliance master curve as a function of time fits a hyperbolic sine equation. The temperature shift factor as a function of the temperature a_T (T) is accurately represented by a general equation based on free volume. A simple relationship between the two parameters of the equation is explored. The viscoelasticity of PVDF is also seen in dynamic mechanical analysis performed at the frequency of 1 Hz. The origin of the viscoelastic character well present in the deformability of the PVDF in service is due to the occurrence of the α_c relaxation that is active at ∼50 °C (E″ peak at 1 Hz).     

Hydrolysis of Fe(OH)SO4 in the presence of metallic iron

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.