Microstructural evidence of the toughening mechanisms of polyurethane reinforced with halloysite nanotubes under high strain-rate tensile loading.

In this study, we have investigated the relationship between the spherulitic morphology and the dynamic tensile response of polyurethane reinforced with Halloysite nanotubes (HNTs). The polyurethane prepolymer is partially silane end-capped and filled with only 0.8 wt.% of acid-treated Halloysite nanotubes. The resultant nanocomposite material presents a 35% higher spall strength compared to the neat polyurethane and 21% higher fracture toughness. We show evidence that the HNTs are not the toughening phase in the nanocomposite, but rather it is their influence on the resultant spherulitic structures which alters the polymer microstructure and leads to a tougher dynamic response. Microstructural characterization is performed via Scanning Electron Microscopy, Atomic Force Microscopy and Field Emission Scanning Electron Microscopy, and crystallinity examination via X-ray diffraction. The spherulitic structures present a brittle fracture character, while the interspherulitic regions are more ductile and show large deformation. The nanocomposite presents a finer and more rigid spherulitic structure, and a more energy dissipative fracture mechanism characterized by a rougher fracture surface with highly deformed interspherulitic regions.

Synthesis and characterization of partially silane-terminated polyurethanes reinforced with acid-treated halloysite nanotubes for transparent armour systems.

In the present work, nanocomposites based on the partially silane-terminated polyurethanes reinforced with sulfuric acid-treated halloysite nanotubes were synthesized and evaluated as a potential candidate for transparent blast resistant configurations. The polyurethane must present high tensile ductility at high strain rates to be able to contain fragments and increase the survivability of the system. Gas-gun spall experiments were conducted to measure the dynamic tensile strength (spall strength) and fracture toughness of the nanocomposite and neat polyurethane. The nanocomposite presented a 35% higher spall strength and 21% higher fracture toughness compared to the neat polyurethane while maintaining transparency. The recovered samples following the spall tests were analysed via scanning electron microscope fractographies. The nanocomposite and neat polyurethane samples were chemically characterized via Fourier transform infrared spectroscopy and melting behaviour via differential scanning calorimetry. The improved properties can be attributed, in large part, to the presence of more rigid spherulitic structures, and a rougher fracture surface constituting of several micro-cracks within the nanocomposite.

Molecular dynamics at constant Cauchy stress.

The Parrinello-Rahman algorithm for imposing a general state of stress in periodic molecular dynamics simulations is widely used in the literature and has been implemented in many readily available molecular dynamics codes. However, what is often overlooked is that this algorithm controls the second Piola-Kirchhoff stress as opposed to the true (Cauchy) stress. This can lead to misinterpretation of simulation results because (1) the true stress that is imposed during the simulation depends on the deformation of the periodic cell, (2) the true stress is potentially very different from the imposed second Piola-Kirchhoff stress, and (3) the true stress can vary significantly during the simulation even if the imposed second Piola-Kirchhoff is constant. We propose a simple modification to the algorithm that allows the true Cauchy stress to be controlled directly. We then demonstrate the efficacy of the new algorithm with the example of martensitic phase transformations under applied stress.

Transiting the molecular potential energy surface along low energy pathways: the TRREAT algorithm.

The Transition Rapidly exploring Random Eigenvector Assisted Tree (TRREAT) algorithm is introduced to perform searches along low curvature pathways on a potential energy surface (PES). The method combines local curvature information about the PES with an iterative Rapidly exploring Random Tree algorithm (LaValle, Computer Science Department, Iowa State University, 1998, TR98-11) that quickly searches high-dimensional spaces for feasible pathways between local minima. Herein, the method is applied to identifying conformational changes of molecular systems using Cartesian coordinates while avoiding a priori definition of collective variables. We analyze the pathway identification problem for alanine dipeptide, cyclohexane and glycine using nonreactive and reactive forcefields. We show how TRREAT-identified pathways can be used as valuable input guesses for double-ended methods such as the Nudged Elastic Band when ascertaining transition state energies. This method can be utilized to improve/extend the reaction databases that lie at the core of automatic chemical reaction mechanism generator software currently developed to build kinetic models of chemical reactions.