Synergism Effect between Nanofibrillation and Interface Tuning on the Stiffness-Toughness Balance of Rubber-Toughened Polymer Nanocomposites: A Multiscale Analysis.

As the design and scalable technology development of tough, yet stiff, polymer nanocomposites receive attention in the automotive industry, fundamental understating of underlying toughening mechanisms at the nanoscale is inevitable. However, mechanical tests on rubber-toughened nanocomposites have shown that their overall fracture properties are significantly smaller than theoretical predictions. Our previous study showed that major factors in this regard are the simultaneous operation of different toughening mechanisms and the nanostructural features of the interface. As a result, it may be necessary to employ multiscale and multimechanism modeling strategies to accurately account for the contribution of each toughening mechanism. In this study, the effects of nanofibrillation (i.e., size, orientation, and dispersion) and interfacial tuning on the mechanical properties of nanofibrillated rubber-toughened nanocomposites are examined using molecular dynamics (MD) simulations. We report that by interfacial modification via grafting compatibilizer at the interface, nanofibrillated rubber-toughened polypropylene (PP) nanocomposite can achieve superior mechanical properties as a result of enhanced interfacial load transfer. Compared to pure ethylene propylene diene monomer rubber (EPDM)/PP system, an increase of 49% in energy absorbed per unit volume during fracture was achieved for 30% functionalized nanocomposites. Such an increase in energy dissipation was caused by a transition in the dominant crack propagation mechanism from interfacial slippage to crack-arresting behavior, owing to enhanced interfacial adhesion. MD simulations in conjunction with the multiscale model revealed that such a change in mechanism is caused by the formation of strong covalent bonds, interfacial friction, and the presence of a highly entangled polymeric network at the interface. Although the multiscale framework can be viewed as a road map for modeling the interface of various nanocomposite systems, the results obtained from our study may offer valuable insights for developing robust and scalable fabrication processes for nanofibrillated rubber-toughened nanocomposite structures, which pose significant technological challenges.

The role of interface on the toughening and failure mechanisms of thermoplastic nanocomposites reinforced with nanofibrillated rubber.

The interface plays a crucial role in the physical and functional properties of polymer nanocomposites, yet its effects have not been fully recognized in the setting of classical continuum-based modeling. In the present study, we investigate the roles of interface and interfiber interactions on the toughening effects of rubber nanofibers embodied in thermoplastic-based materials. Emphasis is placed on establishing comprehensive theoretical and atomistic descriptions of the nanocomposite systems subjected to pull-out and uniaxial extension in the longitudinal and transverse directions. Using the framework of molecular dynamics, the annealed melt-drawn nanofibers were spontaneously formed via the proposed four-step methodology. The generated nanofibers were then crosslinked using the proposed robust topology-matching algorithm, through which the chemical reactions arising in the crosslinking were closely assimilated. The interfiber interactions were also examined with respect to separation distances and nanofiber radius via a nanofiber-pair atomistic scheme, and the obtained results were subsequently incorporated into the pull-out and uniaxial test simulations. The results indicate that the compatibilizer grafting results in enhanced interfacial shear strength by introducing extra chemical interactions at the interface. In particular, it was found that the compatibilizer restricts the formation and coalescence of nanovoids, resulting in enhanced toughening effects. Together, we have shown that the presence of a small amount of well-dispersed rubber nanofibrillar network whose surfaces are grafted with maleic anhydride compatibilizer can dramatically increase the toughness and alter the failure mechanisms of the nanocomposites without any deterioration in the stiffness, which is also consistent with the recent experimental observations in our lab. The interfacial failure mechanism was also investigated by monitoring the changes in the atomic concentration profiles, mean square displacement and fractional free volume. The results obtained may serve as a promising alternative for the continuum-based modeling and analysis of interfaces.

The Effects of Intra-membrane Viscosity on Lipid Membrane Morphology: Complete Analytical Solution.

We present a linear theory of lipid membranes which accommodates the effects of intra-membrane viscosity into the model of deformations. Within the Monge parameterization, a linearized version of the shape equation describing membrane morphology is derived. Admissible boundary conditions are taken from the existing non-linear model but reformulated and adopted to the present framework. We obtain a complete analytical expression illustrating the deformations of lipid membrane subjected to the influences of intra-membrane viscosity. The result predicts wrinkle phenomena in the event of membrane-substrate interactions. Finally, we mention that the obtained solutions reduce to those from the classical shape equation when the viscosity effects are removed.