Shichun Jiang | Searcharxiv

arXiv2023

Mpemba Effect in Crystallization of Polybutene-1

The Mpemba effect and its inverse can be understood as a result of nonequilibrium thermodynamics. In polymers, changes of state are generally non-equilibrium processes. However, the Mpemba effect has been rarely reported in the crystallization of polymers. In the melt, polybutene-1 (PB-1) has the lowest critical cooling rate in polyolefins and tends to maintain its original structure and properties with thermal history. A nascent PB-1 sample was prepared by using metallocene catalysis at low temperature, and the crystallization behavior and crystalline structure of the PB-1 were characterized by DSC and WAXS. Experimentally, a clear Mpemba effect is observed not only in the crystallization of the nascent PB-1 melt in form II but also in form I obtained from the nascent PB-1 at low melting temperature. It is proposed that this is due to the differences in the chain conformational entropy in the lattice which influence conformational relaxation times. The entropy and the relaxation time can be predicted using the Adam-Gibbs equations, whereas non-equilibrium thermodynamics is required to describe the crystallization with the Mpemba effect.

cond-mat.soft↗

arXiv2020

Structure/property relationship of semi-crystalline polymer during tensile deformation: A molecular dynamics approach

A coarse-grained molecular dynamics model of linear polyethylene-like polymer chain system was built to investigate the responds of structure and mechanical properties during uniaxial deformation. The influence of chain length, temperature, and strain rate were studied. The molecular dynamic tests showed that yielding may governed by different mechanisms at temperatures above and below Tg. Melt-recrystallization was observed at higher temperature, and destruction of crystal structures was observed at lower temperatures beyond yield point. While the higher temperature and lower strain rate have similar effects on mechanical properties. The correlated influences of time and temperature in the microscopic structures are more complicated. The evolution of microscopic characteristics such as the orientation parameter, the bond length, and the content of trans-trans conformation were calculated from the simulation. The results showed that the temperature have double effects on polymer chains. Higher temperature on one hand makes the chains more flexible, while on the other hand shortens the relaxation time of polymers. It is the interaction of these two aspects that determine the orientation parameter. During deformation, the trans conformation has experienced a rising process after the first drop process. And these microscopic structure parameters exhibit critical transaction, which are closely related to the yield point. A hypothetical model was thus proposed to describe the micro-structure and property relations based the investigations of this study.

cond-mat.soft↗