Persistence of regions with high segment density in polyethylene melts

Proton nuclear magnetic resonance (NMR) spin-spin relaxation measurements were made on three commercial-grade polyethylenes in the melt state, free of solvent. All samples exhibit a three-component relaxation behavior, with components being assigned to amorphous low-molecular weight material (non-network fraction), amorphous entangled network fraction, and an ordered or high-segmental-density fraction, in order of decreasing relaxation times. Sample thermal history is shown to have a considerable effect on the overall relaxation behavior, and therefore on the relative amounts of each of the three components in the melt. An adequate thermal treatment of samples produces an equilibrium melt with invariant composition of the three fractions. The effects of thermal history on the relative amount of high-segment-density regions in the melt parallels its effect on the fraction of crystalline material in the solid polymer. These results are evidence for the persistence of ordered regions in polyethylene at temperatures well above the crystalline melting point of the polymer. We further comment on the nature of the two slower relaxing components and present examples of how the components manifest themselves in other polymer characterization techniques. © 1992 John Wiley & Sons, Inc.     

Monte carlo studies of phase transitions in polymer blends and block copolymer melts

Summary The unmixing transition of both symmetrical polymer blends AB (i.e. chain lengthsN _A=N _B=N) and asymmetrical ones (N _B/N _A=2,3) is studied by large-scale Monte Carlo simulations of the bond fluctuation model. Combination of semi-grand-canonical simulation techniques, ?histogram reweighting? and finitesize scaling allows an accurate location of the coexistence curve in the critical region. The variation of the critical temperature with chain length (N) is studied and compared to theoretical predictions. For the symmetrical case, use of chain lengths up toN=512 allows a rough estimation of crossover scaling functions for the crossover from Ising to mean-field exponents. The order-disorder transitions in melts of both symmetric (compositionf=N _A/(N _A+N _B)=1/2) and asymmetric (f=3/4) block copolymers is studied for very short chains (16≤N≤60). The interplay between structure and chain configuration is emphasized. Qualitative evidence for ?dumbell formation? of chains and vacancy enrichment in A-B-interfaces and near hard walls is presented. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

Theoretical analysis of non-uniform extensional flows in relation to processing rheology and predictions of some constitutive equations

In this paper, a characteristic equation involving the stream function, already given by one of the authors in a previous work for classifying axisymmetric incompressible flows, is re-considered. Non-uniform nearly extensional flows are derived as particular solutions from this equation. Using experimental data in the literature for polymer solutions and melts, it is proved that particular solutions of the characteristic equation lead to kinematics very close to those encountered in the fiber-spinning process. The kinematic equations satisfactorily correlating the fiber-spinning data are used in order to determine the ability of constitutive equations to predict realistic stresses in the flow domain. The rheological parameters of the fluids, obtained from experiments, are used for computation of differential and integral constitutive equations in the spinning conditions. Comparisons with the stress response of adequate constitutive equations are given and discussed.Also affiliated to: Université Joseph Fourier Grenoble I and Institut National Polytechnique de Grenoble, Associé au CNRS (URA 1510)     

On the viscosity-temperature behavior of polymer melts

Based on the free volume concept and the equation by Doolittle, an empirical equation is offered for the flow activation energy, E ^*, for polymer melts for the range of over 150°C above glass transition temperature, T _g. This E ^* represents the temperature coefficient of viscosity for the Newtonian region which is also equal to the value measured at constant shear stress for non-Newtonian flow. Data show that the E ^* of linear polymers approaches a constant value for a temperature range above T _g+150°C. Data on 17 polymers are correlated. The proposed equation for this region predicts the E ^* of polymer melts from the volume expansion coefficient, _l, above T _g and also from the T _g.Correlations have also been developed between E ^* and _l and between E ^* and T _g by simplifying the equation by use of the Simha-Boyer expression. A polymer having a lower _l or higher T _g generally has a higher E ^*. However, more satisfactory results are obtained by calculating E ^* from both _l and T _g. The E ^* calculated is found to agree with measurements within the experimental precision of about ±1 Kcal/mole.The effects of polymer composition, molecular weight, branching and microstructure on E ^* are also discussed. These factors influence E ^* in the way in which they effect _l and T _g.     

A network model with free-strand dynamics for polymer melts

 A network model for polymer melts is presented in which disentangled strands relax under flow conditions and may rejoin the network before complete relaxation. For simplicity, we study Gaussian strands that move affinely when incorporated in the network. Network strands are created and lost according to a time constant λ. Free strands have their dynamics given by the Bird-DeAguiar model as a crude representation of reptation and the hindered rotation experienced by polymer strands in melts. The model yields a shear-thinning viscosity with overshoot in the start-up viscosity η⁺ (t). The double-step strain results compare well with available experimental data. Received: 10 July 2000 Accepted: 10 July 2001     

The “decaying springs” model for irreversibility in polymer melts

In this work, entanglements in a polymer melt are modeled as a system of parallel springs which form and decay spontaneously. The springs are assumed to be nonlinear, and a certain fraction of them is torn apart by a certain strain.Based on these assumptions, a model of behavior in simple shear is developed. This model is shown to predict a behavior comprising that of a Wagner fluid, and is generalized to a tensorial model of single integral type. The integrand depends on a product of a material function, modeling reversible behavior, and a material functional which takes irreversible processes into account.Irreversibility of network disentanglement, which may occur when deformation changes or reverses direction, can be modeled in this way. It is shown that the two well-known Wagner constitutive equations with and without irreversibility assumptions are special cases of the model developed. In case of a deformation which does not change directions, the new material function and the material functional are multiplied to yield Wagner's damping function.When the rate of spring formation is a function of temperature, the developed model is shown to predict thermorheologically simple behavior. A constitutive equation for non-isothermal flow of polymers is developed with this assumption.     

Numerical simulation of large amplitude oscillatory shear of a high-density polyethylene melt using the MSF model

We study the flow response in large amplitude oscillatory shear of the molecular stress function (MSF) model that has recently been proposed by Wagner et al. [M.H. Wagner, P. Rubio, H. Bastian, The molecular stress function model for polydisperse polymer melts with dissipative convective constraint release, J. Rheol. 45 (2001) 1387–1412]. The MSF model is derived from molecular theory and has only two parameters to describe the non-linear material response. The model predictions are analysed in both the frequency and time domain. It shows good agreement with experimental data for a linear high-density polyethylene melt. At low and medium strains, MSF model predictions are in excellent agreement with experimental data and predictions of a six-mode Giesekus model which has six parameters to describe the non-linear material response. At medium strains, the basic Doi–Edwards model, which has no non-linear parameters, already underpredicts the data. At high strains, the MSF model predictions agree slightly better with the experimental data than the Giesekus model. Surprisingly, however, it is the Doi–Edwards model that shows excellent agreement with experimental data at high strains. For the linear melt we consider, it outperforms the models that have non-linear parameters, both in the time and frequency domain.     

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