Microstructural Dynamics of Polymer Melts during Stretching: Radial Size Distribution.

The transient elongational viscosity ηe(t) of the polymer melt is known to exhibit strain hardening, which depends on the strain rate ε˙. This phenomenon was elucidated by the difference of chain stretching in the entanglement network between extension and shear. However, to date, the microscopic evolution of polymer melt has not been fully statistically analyzed. In this work, the radial size distributions P(Rg,t) of linear polymers are explored by dissipative particle dynamics during the stretching processes. In uniaxial extensional flow, it is observed that the mean radius of gyration R¯g(t) and standard deviation σ(t) remain unchanged until the onset of strain hardening, corresponding to linear viscoelasticity. Both R¯g and σ rise rapidly in the non-linear regime, and bimodal size distribution can emerge. Moreover, the onset of strain hardening is found to be insensitive to the Hencky strain (ε˙Ht) and chain length (N).

Thermally assisted mobility of nanodroplets on surfaces with weak defects.

HYPOTHESIS: Thermal activation plays an essential role in contact line dynamics on nanorough surfaces. However, the relation between the aforementioned concept and the sliding motion of nanodroplets remains unclear. As a result, thermally assisted motion of nanodroplets on nanorough surfaces is investigated in this work. EXPERIMENTS: Steady slide and random motion of nanodroplets on surfaces with weak defects are investigated by Many-body Dissipative Particle Dynamics. The surface roughness is characterized by the slip length acquired from the velocity profile associated with the flowing film. FINDINGS: The slip length is found to decline with increasing the defect density. The linear relationship between the sliding velocity and driving force gives the mobility and reveals the absence of contact line pinning. On the basis of the Navier condition, a simple relation is derived and states that the mobility is proportional to the slip length and the reciprocal of the product of viscosity and contact area. Our simulation results agree excellently with the theoretical prediction. In the absence of external forces, a two-dimensional Brownian motion of nanodroplets is observed and its mean square displacement decreases with increasing the defect density. The diffusivity is proportional to the mobility, consistent with the Einstein relation. This consequence suggests that thermal fluctuations are able to overcome contact line pinning caused by weak defects.

Size-dependence and interfacial segregation in nanofilms and nanodroplets of homologous polymer blends.

The size-dependent behavior of nanofilms and nanodroplets of homologous polymer blends was explored by many-body dissipative particle dynamics. Although a homologous blend can be regarded as a completely miscible and athermal system, enrichment of the surface in short polymers always takes place. First, liquid-gas and solid-liquid interfacial tensions of polymer melts were acquired. It is found that they increase and approach asymptotes with increasing chain lengths. The molecular weight dependence can be depicted using two semi-empirical expressions. Second, the variation of surface tension and surface excess of polymer blend nanofilms with the thickness was observed. Surface tension of the blend is observed to increase but the extent of surface segregation decreases upon increasing the film thickness. Finally, the wetting phenomenon of nanodroplets of homologous blends was examined. The contact angle is found to increase as the droplet size is reduced. Our simulation results indicate that the size-dependence of nanofilms and nanodroplets is closely related to surface segregation in homologous blends.