Nucleation and growth of crystals inside polyethylene nano-droplets

H Zerze, JOURNAL OF CHEMICAL PHYSICS, 157, 154901 (2022).

DOI: 10.1063/5.0105466

Polymer crystallization is a long-standing interesting problem both in fundamental polymer physics and in polymer manufacturing. Fundamentally, the connectivity of the macromolecules provides a unique feature for the study of nucleation and growth of crystals in contrast to the crystallization of smaller molecules. In addition, understanding the crystallization in polymers is industrially important due to the necessity of its control to achieve mechanically durable plastic materials. Molecular dynamics simulations offer a suitable way of studying this phenomenon due to their capability to probe the small time and length scales that are characteristic of nucleation. In this paper, we use a long alkane chain model to study nucleation and the growth of polyethylene crystals both within bulk and nano-droplets whose diameters range from about 6 to 11 nm. It is found that the droplets approach being more spherical during the nucleation whereas they deviate from this shape during the growth regime. Strikingly, a mean first passage time analysis indicates that the nucleation rate per unit volume decreases as the droplet size is increased. Finally, visual inspection of the simulation snapshots suggests that nuclei majorly emerged from the surface of the droplets. Published under an exclusive license by AIP Publishing.

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