Preparation and Characterization of High-Density Polyethylene with Alternating Lamellar Stems Using Molecular Dynamics Simulations.

Mechanical recycling is the most efficient way to reduce plastic pollution due to its ability to maintain the intrinsic properties of plastics as well as provide economic benefits involved in other types of recycling. On the other hand, molecular dynamics (MD) simulations provide key insights into structural deformation, lamellar crystalline axis (c-axis) orientations, and reorganization, which are essential for understanding plastic behavior during structural deformations. To simulate the influence of structural deformations in high-density polyethylene (HDPE) during mechanical recycling while paying attention to obtaining an alternate lamellar orientation, the authors examine a specific way of preparing stacked lamella-oriented HDPE united atom (UA) models, starting from a single 1000 UA (C(1000)) chain of crystalline conformations and then packing such chain conformations into 2-chain, 10-chain, 15-chain, and 20-chain semi-crystalline models. The 2-chain, 10-chain, and 15-chain models yielded HDPE microstructures with the desired alternating lamellar orientations and entangled amorphous segments. On the other hand, the 20-chain model displayed multi-nucleus crystal growth instead of the lamellar-stack orientation. Structural characterization using a one-dimensional density profile and local order parameter {P(2)(r)} analyses demonstrated lamellar-stack orientation formation. All semi-crystalline models displayed the total density (ρ) and degree of crystallinity (χ) range of 0.90-0.94 g/cm(-3) and ≥42-45%, respectively. A notable stress yield (σ_yield) ≈ 100-120 MPa and a superior elongation at break (ε_break) ~250% was observed under uniaxial strain deformation along the lamellar-stack orientation. Similarly, during the MD simulations, the microstructure phase change represented the average number of entanglements per chain (). From the present study, it can be recommended that the 10-chain alternate lamellar-stack orientation model is the most reliable miniature model for HDPE that can mimic industrially relevant plastic behavior in various conditions.