金属熔体黏度与结构相关性的分子动力学模拟

运用EAM(embed atom method)作用势，采用非平衡分子动力学模拟获得Al熔体的偶分布函数与黏度数值随温度的变化曲线，偶分布函数的计算结果与实验值符合得较好.对模拟所得到的黏度数据编程实现黏度的Arrhenius公式拟合，得到激活能E.并利用模拟所得到的黏度值及激活能对Lennard-Jones(L-J)作用势进行修正，获得黏度与偶分布函数及原子间相互作用势之间的关系式，两条黏度拟合曲线与分子动力模拟结果符合得比较好，说明拟合程序的编写是比较成功的，实现了对L-J作用势的修正.该研究为金属及合金原子间相互作用势的建立提供了新的思路. 关键词： 非平衡分子动力学模拟 L-J作用势修正 Al熔体 结构与黏度相关性     

Frequency and molecular-mass-dependent nonexponential proton NMR relaxation in polymer melts

A theoretical treatment of the nonexponential relaxation behavior of the different proton nuclear magnetic resonance (NMR) relaxation processes in polymer melts is presented. Formulas are derived for a three-component model given by two versions and a homogeneous distribution of correlation times. The theoretical results were tested with measurements of T₁, T_2e, and T₂ as functions of frequency and molecular mass in linear fractionated polyethylene samples. While the T₁ relaxation always yields exponential magnetization decays, the T_2e and T₂ measurements show biexponential relaxation behavior. From the calculations it was found that the correlation time of the local motion is independent of the molecular mass, whereas the correlation time of the slowest motional process increases with M^2.8_w for the three-component model and with M^2.2_w for the distribution of correlation times, respectively. © 1992 John Wiley & Sons, Inc.     

The lamellar-disorder interface: one-dimensional modulated profiles

We study interfacial behavior of a lamellar (stripe) phase coexisting with a disordered phase. Systematic analytical expansions are obtained for the interfacial profile in the vicinity of a tricritical point. They are characterized by a wide interfacial region involving a large number of lamellae. Our analytical results apply to systems with one dimensional symmetry in true thermodynamical equilibrium and are of relevance to metastable interfaces between lamellar and disordered phases in two and three dimensions. In addition, good agreement is found with numerical minimization schemes of the full free energy functional having the same one dimensional symmetry. The interfacial energy for the lamellar to disordered transition is obtained in accord with mean field scaling laws of tricritical points. Received: 28 March 1997 / Revised: 6 February 1998 / Accepted: 16 February 1998     

Density of stratified ionic melts: Experiment and theory

Densities of phases co-existing in molten ionic systems with partial miscibility out of halides of alkali metals (KBr, KI, RbBr, RbI, CsCl, CsBr, CsI) with lithium fluoride are determined in a broad temperature interval by a method of hydrostatic weighing. A linear decrease in the difference between phase densities with increasing temperature is found for all systems. By studying a molten KBr-LiF mixture, this regularity is traced up to a critical miscibility point. The critical index of the order parameter, calculated from these data happens to equal 1/2 and coincide with results predicted by mid-field theory.     

Densities of Melts of the System KF?K2MoO4?B2O3

The density of melts of the system KF? K₂MoO₄? B₂O₃ was measured. The molar volume in the binary system KF? K₂MoO₄ deviates only little from the ideal course, which indicates the extended thermal dissociation of the congruently melting additive compound K₃FMoO₄. In the KF? B₂O₃ binary system the formation of KBF₄ and K₂B₄O₇ leads to the volume expansion, like in the K₂MoO₄? B₂O₃ system, where the volume expansion may be described by the formation of the heteropolyanions [BMo₆O₂₄]^9?. The significant deviation from the ideal behaviour in the ternary system KF? K₂MoO₄? B₂O₃ refers to the pronounced interaction, most probably due to the substitution of oxygen atoms in the coordination sphere of the heteropolyanion with the fluorine ones.     

Diffusion of ethylene glycol accompanied by reactions in poly(ethylene terephthalate) melts

Diffusion coefficients of ethylene glycol (EG) have been measured in poly(ethylene terephthlate) (PET) melts by a quartz-spring sorption apparatus. A simple mathematical model was developed to investigate the sorption behavior accompanied by chemical reactions of EG and PET at high temperatures. Diffusion coefficients are deduced from experimental data for an asymptotically thin sample in order to minimize the effects of reactions. The diffusion coefficient of EG is strongly dependent on the vapor pressure of EG and temperature but not on the molecular weight of PET in this experimental range (degree of polymerization 80–120). The diffusion coefficient of EG in PET melt at 265°C is 2.58 × 10^?7 cm²/s at the limit of zero concentration of EG. The activation energy for diffusion is 38.4 kcal/gmol, and the heat of solution for sorption is ?44.9 kcal/gmol. The concentrations of the volatile materials resulting from reactions in PET-EG system were analyzed with gas chromatography. In addition, a fit of the current model to experimental data yields frequency factors for the polymerization reaction (k₁) and the acetaldehyde formation reaction (k₂) to be 5.84 × 10⁸ cm³/mol ? min and 3.90 × 10¹¹ min^?1, respectively.     

Capillary and slit-die flow of two liquid-crystalline polymers. The effect of pressure on viscosity

Viscosity measurements on two commercial thermotropic liquid crystalline polymers (LCPs) (a copolyester and a polyesteramide) were performed using both capillary and slit die methods. The results are in agreement with those presented in the literature for the same LCPs, when the measurements are carried out with a L/D = 30 die; these results are affected more by Bagley corrections for the polyesteramide than for the copolyester. For both LCPs, viscosities measured in the slit die are lower than those obtained by capillary rheometry. Nevertheless, the difference is much bigger in the case of the polyesteramide, for which a reduction by a factor of 3 is observed. This is not due to the preshear or thermal history, since the same piston-barrel system and thermal treatment were applied in both types of measurements. Depending on the polymer sample and temperature, concave and convex curvatures were observed in the pressure profiles during the slit flow. From these curvatures, the pressure coefficient α of viscosity was evaluated. However, in the case of the polyesteramide the convex curvature leads to a negative coefficient (the viscosity decreases with pressure, instead of increasing). This result may be explained by envisaging a change in the structure of the melt along the slit length. © 1993 John Wiley & Sons, Inc.     

The effect of stiffness in wormlike micelles

The effect of stiffness in a 2D living polymer system is investigated by Monte-Carlo simulation in a canonical ensemble. As the flexibility decreases, the mean chain contour length decreases and goes through a local maximum. The mean end to end square distance shows a non-monotonic behaviour due to the coil-to-rod transition and the decrease in chain contour length. Near the maximum of chain ordering in the bulk, the chain length distribution adapts itself to increase the configurational entropy. With the parameters used in this simulation, it seems that the effect of the stiffness for high stiffness is to decrease as in the isotropic case, since the ordering decreases again. Received: 16 September 1997 / Revised: 27 June 1998 / Accepted: 29 June 1998     

Phase behaviour of a dispersion of charge-stabilised colloidal spheres with added non-adsorbing interacting polymer chains

We present a theory for the phase behaviour of mixtures of charge-stabilised colloidal spheres plus interacting polymer chains in good and θ -solvents within the framework of free-volume theory. We use simple but accurate combination rules for the depletion thickness around a colloidal particle and for the osmotic pressure up to the semi-dilute concentration regime. Hence, we obtain expressions for the free energy for mixtures of charged colloidal particles and non-adsorbing interacting polymers. From that, we calculate the phase behaviour, and discuss its topology in dependence on the competition between the charge-induced repulsion and the polymer-induced attraction. The homogeneous mixture of colloids and polymers becomes more stabilised against demixing when increasing the electrostatic repulsion. This charge-induced stabilisation is strongest for small polymer-to-colloid size ratios and is more pronounced for charged colloids mixed with polymers in a good solvent than for polymers in a θ -solvent. For the weakly charged regime we find that the phase diagram becomes salt-concentration-independent in the protein limit for charged colloids plus polymers in a θ -solvent. The liquid window, i.e., the concentration regimes where a colloidal liquid exists, is narrowed down upon increasing the charge-induced repulsion. Also this effect is more pronounced when charged colloids are mixed with polymer chains in a good solvent. In summary, we demonstrate that the solvent quality significantly influences the phase behaviour of mixtures of charged colloids plus non-adsorbing polymers if the range of the screened electrostatic repulsion becomes of the order of the range of the depletion-induced attraction.     

Simple Estimates for Eutectic Behavior

A simple formula is derived for the eutectic point of an A–B system in terms of the monomer melting points and melting enthalpies. This estimate is tested on several non-ionic or ionic systems, with or without common ions, including choline chloride/urea mixtures. The results are compared with the Schröder-van Laar equation.