Molecular Simulation of Flow-Enhanced Nucleation in n-Eicosane Melts Under Steady Shear and Uniaxial Extension

Non-equilibrium molecular dynamics is used to study crystal nucleation of n-eicosane under planar shear and, for the first time, uniaxial extension. A method of analysis based on the mean first-passage time is applied to the simulation results in order to determine the effect of the applied flow field type and strain rate on the steady-state nucleation rate and a characteristic growth rate, as well as the effects on kinetic parameters associated with nucleation: the free energy barrier, critical nucleus size, and monomer attachment pre-factor. The onset of flow-enhanced nucleation (FEN) occurs at a smaller critical strain rate in extension as compared to shear. For strain rates larger than the critical rate, a rapid increase in the nucleation rate is accompanied by decreases in the free energy barrier and critical nucleus size, as well as an increase in chain extension. These observations accord with a mechanism in which FEN is caused by an increase in the driving force for crystallization due to flow-induced entropy reduction. At high applied strain rates, the free energy barrier, critical nucleus size, and degree of stretching saturate, while the monomer attachment pre-factor and degree of orientational order increase steadily. This trend is indicative of a significant diffusive contribution to the nucleation rate under intense flows that is correlated with the degree of global orientational order in a nucleating system. Both flow fields give similar results for all kinetic quantities with respect to the reduced strain rate, which we define as the ratio of the applied strain rate to the critical rate. The characteristic growth rate increases with increasing strain rate, and shows a correspondence with the nucleation rate that does not depend on the type of flow field applied. Additionally, a structural analysis of the crystalline clusters indicates that the flow field suppresses the compaction and crystalline ordering of clusters, leading to the formation of large articulated clusters under strong flow fields, and compact well-ordered clusters under weak flow fields

Real-time depth sectioning: Isolating the effect of stress on structure development in pressure-driven flow

Transient structure development at a specific distance from the channel wall in a pressure-driven flow is obtained from a set of real-time measurements that integrate contributions throughout the thickness of a rectangular channel. This “depth sectioning method” retains the advantages of pressure-driven flow while revealing flow-induced structures as a function of stress. The method is illustrated by applying it to isothermal shear-induced crystallization of an isotactic polypropylene using both synchrotron x-ray scattering and optical retardance. Real-time, depth-resolved information about the development of oriented precursors reveals features that cannot be extracted from ex-situ observation of the final morphology and that are obscured in the depth-averaged in-situ measurements. For example, at 137 °C and at the highest shear stress examined (65 kPa), oriented thread-like nuclei formed rapidly, saturated within the first 7 s of flow, developed significant crystalline overgrowth during flow and did not relax after cessation of shear. At lower stresses, threads formed later and increased at a slower rate. The depth sectioning method can be applied to the flow-induced structure development in diverse complex fluids, including block copolymers, colloidal systems, and liquid-crystalline polymers

On the flow birefringence of polypropylene in solution

The flow birefringence of solutions of two samples of polypropylene is investigated. Trans-decalin is chosen as a solvent. The measuring temperature is 150 °C. The viscometric molecular weight of the samples is nearly the same, whereas the breadth of the molecular weight distribution is very different. The value of the apparent coil expansion, as calculated from flow birefringence data, is in particular very sensitive to the shape of the distribution function in the high molecular weight region. Conclusions are drawn as to the difference in skewness of the distributions of the two samples investigated. © 1966 Dr. Dietrich Steinkopff Verlag