Stress relaxation in entangled melts of unlinked ring polymers

Stress relaxation in unlinked ring polymer melts poses an important challenge to our theoretical understanding of entangled polymer dynamics. Recent experiments on entangled unlinked ring melts show power-law stress relaxation with no hint of a rubbery plateau, usually the hallmark of entangled polymers. Here we present a theory for stress relaxation in rings analogous to the successful approach for star polymers. We augment our theory with mesoscale Monte Carlo dynamics simulations of equivalent "lattice animal" configurations. We find a stress relaxation function G(t)～t(-α) with α≈1/2 consistent with experiment, emerging ultimately from the disparate relaxation times of more- and less-central portions of ring conformations.     

利用单分子光学探针测量幂律分布的聚合物动力学

研究聚合物薄膜纳米尺度的动力学特性对于高性能材料的制备具有重要的意义.本文利用尼罗红单分子作为光学探针吸附在聚丙烯酸甲酯(PMA)聚合物链上,研究该聚合物薄膜的动力学特性.通过单分子散焦宽场荧光成像显微镜技术测量了单分子随PMA聚合物链转动弛豫的三维再取向特性,当环境温度高于PMA的玻璃点温度19 K时,发现处于PMA聚合物薄膜中的单分子光学探针的转动态和非转动态的持续时间概率密度服从指数截止的幂律分布.研究结果表明该温度下PMA聚合物薄膜的纳米环境动力学仍存在空间和时间异构性.     

Modeling viscoelastic flow with discrete methods

The hydrodynamics of viscoelastic materials (for example, polymer melts and solutions) presents interesting and complex phenomena, for example, instabilities and turbulent flow at very low Reynolds numbers due to normal stress effects and the existence of a finite stress relaxation time. This present work is motivated by renewed interest in instabilities in polymer flow. The majority of currently used numerical methods discretize a constitutive equation on a grid with finite difference or similar methods. We present work in progress in which we simulate viscoelastic flow with dissipative particle dynamics. The advantage of this approach is that many of the numerical instabilities of conventional methods can be avoided, and that the model gives clear physical insight into the origins of many viscoelastic flow instabilities.     

On the dynamics and disentanglement in thin and two-dimensional polymer films

We present results from molecular dynamics simulations of strictly two-dimensional (2D) polymer melts and thin polymer films in a slit geometry of thickness of the order of the radius of gyration. We find that the dynamics of the 2D melt is qualitatively different from that of the films. The 2D monomer mean-square displacement shows a t^8/15 power law at intermediate times instead of the t^1/2 law expected from Rouse theory for nonentangled chains. In films of finite thickness, chain entanglements may occur. The impact of confinement on the entanglement length N_e has been analyzed by a primitive path analysis. The analysis reveals that N_e increases strongly with decreasing film thickness.     

Unusual behaviour of poly(ethylene-oxide) in aqueous mixtures

The model system of poly(ethylene-oxide) or PEO, where the changing hydrogen-bond connectivity of the water has large effect on the conformation of the polymer chain, in mixtures of water and acetonitrile, is experimentally studied. The results show the existence of a threshold water content in the system at which the 3d connectivity of the water network begins. Unusual expansion of the polymer chain, an effect larger than that observed in either of the pure solvents, is seen. Upon addition of small amounts of a monovalent salt, binding of ion to polymer takes place in pure acetonitrile solutions. Salt ions begin to co-ordinate with water molecules at the same solvent ratio as the threshold for water network formation. Ions now no longer complex to PEO; instead, hydrogen bonding of water to the polymer strongly dictates conformation in this regime.Received: 10 September 2004, Published online: 3 November 2004PACS: 61.25.Hq Macromolecular and polymer solutions; polymer melts; swelling - 61.12.Ex Neutron scattering techniques (including small-angle scattering) - 36.20.Ey Conformation (statistics and dynamics)     

Temperature behavior of the Kohlrausch exponent for a series of vinylic polymers modelled by an all-atomistic approach

The Kohlrausch-Williams-Watt (KWW) function, or stretched exponential function, is usually employed to reveal the time dependence of the polymer backbone relaxation process, the so-called α relaxation, at different temperatures. In order to gain insight into polymer dynamics at temperatures higher than the glass transition temperature T _g , the behavior of the Kohlrausch exponent, which is a component of the KWW function, is studied for a series of vinylic polymers, using an all-atomistic simulation approach. Our data show very good agreement with published experimental results and can be described by existing phenomenological models. The Kohlrausch exponent exhibits a linear dependence with temperature until it reaches a constant value of 0.44, at 1.26T _g , revealing the existence of two regimes. These results suggest that, as the temperature increases, the dynamics progressively change until it reaches a plateau. The non-exponential character then describes subdiffusive motion characteristic of polymer melts.     

Anomalous diffusion of a polymer chain in an unentangled melt

Contrary to common belief, hydrodynamic interactions in polymer melts are not screened beyond the monomer length and are important in transient regimes. We show that viscoelastic hydrodynamic interactions (VHIs) lead to anomalous dynamics of a tagged chain in an unentangled melt at t相似文献   

Spontaneous breakup of extended monodisperse polymer melts

We apply continuum mechanical based, numerical modeling to study the dynamics of extended monodisperse polymer melts during the relaxation. The computations are within the ideas of the microstructural "interchain pressure" theory. The computations show a delayed necking resulting in a rupture, as a result of small initial sample imperfections. These ruptures agree with experimental observations.     

Effect of polymer architecture and ionic aggregation on the scattering peak in model ionomers

We perform molecular dynamics simulations of coarse-grained ionomer melts with two different architectures. Regularly spaced charged beads are placed either in the polymer backbone (ionenes) or pendant to it. The ionic aggregate structure is quantified as a function of the dielectric constant. The low wave vector ionomer scattering peak is present in all cases, but is significantly more intense for pendant ions, which form compact, discrete aggregates with liquidlike interaggregate order. This is in qualitative contrast to the ionenes, which form extended aggregates.     

Mode-coupling theory for structural and conformational dynamics of polymer melts

A mode-coupling theory for dense polymeric systems is developed which unifyingly incorporates the segmental cage effect relevant for structural slowing down and polymer chain conformational degrees of freedom. An ideal glass transition of polymer melts is predicted which becomes molecular-weight independent for large molecules. The theory provides a microscopic justification for the use of the Rouse theory in polymer melts, and the results for Rouse-mode correlators and mean-squared displacements are in good agreement with computer simulation results.     

Dynamical theory of polymer melt morphology

A general kinetic equation of the monomer density variables for polymer blends and block copolymer melts is obtained which describes slow morphology variations. The general theory is applied to a polymer blend adopting the biased reptation model of a polymer chain under mean field. We obtain an equation of motion of interfaces in a phase-separated polymer blend, which contains an interface reaction term for length scales shorter than l_c ≡ R²_G/ξ, where R_G is the gyration radius of a polymer chain and ξ the interfacial width. We also discuss some problems associated with the incompressibility requirement for phase separation kinetics of binary systems not limited to polymers. For length scales greater than l_c the interface dynamics involves diffusion in bulk pure phases even in the strong segregation limit in a way different from that for the usual time-dependent Ginzburg-Landau equation for the conserved order parameter. Implications of the existence of the new term on the late stage phase separation kinetics of polymer blend are discussed.A phenomenological model to study morphology dynamics not relying on the reptation model is also proposed.     

Up-Hill Diffusion of Phase-Separated FeCu Melt by Molecular Dynamics Simulation

Molecular dynamics simulation is performed to characterize the concentration fluctuation of FeCu melts during the liquid-liquid phase separation process, which undergoes the following stages: the formation of interconnected structure and its coarsening, migration and coagulation of droplets driven by the decreasing of potential energy.The up-hill diffusion happens at the early relaxation period in which Cu atoms in Fe-rich region are forced to move toward Cu-rich region by spinodal decomposition with 90% Cu content in Cu-rich region and 95% Fe content in Fe-rich region at temperature of 1500 K. The higher diffusion rate of homogeneous atom can be observed at lower temperature, which is attributed to the larger potential energy difference between Cu-rich region and Fe-rich region. It also exhibits energy heterogeneity in the separated liquid. The domain size decreases sharply during the aggregation and coarsening of droplets, after that it keeps unchanged until the coagulation of droplets begins.The studies characterize concentration and energy heterogeneity of phase-separated liquid on the atomic scale.     

模耦合理论计算纳米粒子在聚合物熔体中的含时扩散系数与常规扩散常数 (cited: 2)

分析和计算了纳米粒子在聚合物熔体中的含时扩散系数与常规扩散常数. 采用广义朗之万方程描述扩散动力学,并通过模耦合理论计算摩擦记忆内核.为简单起见,只考虑了来自两体碰撞和溶剂密度涨落耦合作用两类微观因素对摩擦记忆内核的贡献. 采用聚合物参考作用点模型以及Percus-Yevick闭合条件计算了聚合物-纳米粒子复合溶液的平衡态结构信息函数;详尽分析了纳米粒子的尺寸与聚合物链的尺寸对扩散动力学的影响. 揭示了结构函数、摩擦记忆内核以及扩散系数等随着纳米粒子半径和聚合物链长的变化关系. 结果表明,对于小尺寸的纳米粒子或者短链的聚合物,短时间的非马尔可夫扩散 动力学特征比较显著,含时扩散系数需要更长的时间弛豫到常规扩散常数. 微观因素对扩散常数的贡献随着纳米粒子尺寸的增加而减小,却随着聚合物链长的增加而增大. 此外,模耦合理论得到的扩散常数与Stokes-Einstein关系的预测值进行比较,发现对于小尺寸的纳米粒子或者长链的聚合物,微观因素对扩散常数的的贡献占主导地位. 相反,当纳米粒子较大或者聚合物链长较短时,流体力学的贡献会发挥重要作用.     

The frozen state in the liquid phase of side-chain liquid-crystal polymers

Quenched isotropic melts of side-chain liquid-crystal polymers reveal surprisingly an anisotropic polymer conformation. This small-angle neutron-scattering (SANS) result is consistent with the identification of a macroscopic, solidlike response in the isotropic phase. Both experiments (rheology and SANS) indicate that the polymer system appears frozen on millimeter length scales and at the time scales of the observation. This result implies that the flow behavior is not the terminal behavior and that cross-links or entanglements are not a necessary condition to provide elasticity in melts.     

Multidimensional 2H NMR study of dynamical heterogeneity in polymer nanocomposites

Nanoconfined polymer chains-as can be formed when polymers intercalate into layered inorganic materials-show remarkable bulk properties, many of which are connected to dynamical heterogeneity in the polymeric phase. Microscopically, it appears that slow dynamical modes are associated with the species in direct contact with the surface, with substantially more mobile species only a fraction of a nm away. In the more distant phase, larger angle and moderately fast dynamics (typically, ns-micros) grows in over a broad temperature range not well correlated to bulk phase transitions. In this work, we probe the slowest dynamical modes and apply one- and two-dimensional (2)H exchange NMR experiments to study thin polymer layers intercalated between the flat inorganic faces of fluorohectorite (FH). One sample is created by intercalation of perdeuterated poly(ethylene oxide) into FH, and the second by intercalation of d(3)-poly(styrene) into a surface-modified FH. Large-amplitude reorientation of the PEO backbone is substantially hindered in the narrow two-dimensional layers, and reorientation is limited to small-amplitude steps at rates that are largely independent of temperature. Simulations of the two-dimensional exchange experiments suggest that dynamics in nanoconfined polymers is associated with small-angle rotational diffusion.     

Annealing polyelectrolytes at charged interfaces

The conformation of a weakly dissociating (annealing) polyelectrolyte chain end-tethered to a similarly or oppositely charged planar surface is analyzed in the framework of scaling arguments. For a similarly charged interface an analytical model is also utilized. We demonstrate that at low salt concentration in bulk solution there is a strong coupling between the polyelectrolyte conformation and its degree of ionization. In the case of an oppositely charged (adsorbing) surface, adsorption promotes ionization of the annealing polyelectrolyte. As a result, the adsorbed layer thickness decreases as a function of surface charge density more rapidly for an annealing polyelectrolyte than for a quenched one. In the case of a similarly charged (repulsive) surface the chain ionization is suppressed, and the annealing polyelectrolyte chain is less extended than the quenched one. Moreover, an increase in surface charge density leads to non-monotonous extension of the tethered polyelectrolyte.Received: 16 September 2003, Published online: 5 February 2004PACS: 61.25.Hq Macromolecular and polymer solutions; polymer melts; swelling - 82.35.Gh Polymers on surfaces; adhesion - 82.35.Rs Polyelectrolytes     

Experimental verification of the formation mechanism for pillar arrays in nanofilms subject to large thermal gradients

The free surface of molten nanofilms is known to undergo spontaneous formation of periodic protrusions when exposed to a large transverse thermal gradient. Early time measurements of the array pitch and growth rate in polymer melts confirm a formation process based on a long wavelength thermocapillary instability and not electrostatic attraction or acoustic phonon driven growth as previously believed. We find excellent agreement with theoretical predictions provided the nanofilm out-of-plane thermal conductivity is several times larger than bulk, an enhancement suggestive of polymer chain alignment.