화학공학소재연구정보센터
Macromolecules, Vol.46, No.19, 7977-7988, 2013
Short-Range Order in Polyethylene Melts: Identification and Characterization
Experimental results by Fisher et al. [Faraday Discuss. Chem. Soc. 1979, 68, 26] showed the existence of local orientational correlations of segments of the n-alkane molecules in the liquid state. Since the estimated correlation volume is below 10(3) angstrom(3), molecular dynamics simulations appear to be a suitable method for their identification and characterization. We used molecular dynamics to fully characterize short-range order in polyethylene melts. The characterization started by identifying sequences of aligned segments in chains, each one having at least one Kuhn monomer in length. Afterward, a search was made for interactions of a tagged aligned chain segment with others fulfilling the same condition, laying within a limiting separation distance (18 angstrom) and making a limiting orientation angle (40 degrees). When, at least, four interactions are counted, a short-range ordered region is defined. Chain placement in these regions has similarities to that of the unit cell at the solid phase, although with different separation distances and angle. Overall, short-range order resembles a dynamic uniaxial nematic phase, the local order parameter increasing with the chain length in agreement with experimental results. Segments at the ordered regions persist over time, for times longer than the Rouse relaxation time of the chain. Those in random conformational sequences between the ordered regions have a mass distribution in agreement with the Flory distribution, with a number-average value comparable to experimental results for the molecular mass between entanglements.