Abstract
The segregation of the low-molecular-weight fractions on the crystal growth of polydisperse polymers has been identified as a general phenomenon by means of dynamic Monte Carlo simulations of lattice polymer systems. Its mechanism was elucidated on the basis of the intramolecular nucleation model. A unified scheme has been proposed to interpret all three scenarios of molecular segregation according to the location of the crystallization temperature Tc demarcated by two melting points of short-chain fractions, namely for the bulk extended-chain crystals and Tm2D for two-dimensional single-folded-chain crystals on a smooth crystal-growth front. In the first scenario, Tc > , and short-chain fractions are thermodynamically forbidden in crystallization, like the small solvents in conventional monotectic polymer solutions. In the second scenario, > Tc > Tm2D, and short-chain fractions are fully excluded by their failures on the intramolecular secondary nucleation for folded-chain crystal growth. In the third sc...
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