We present a molecular dynamics simulation study of crystal nucleation from
undercooled melts of n-alkanes, and we identify the molecular mechanism of
homogeneous crystal nucleation under quiescent conditions and under shear flow.
We compare results for n-eicosane(C20) and n-pentacontahectane(C150), i.e. one
system below the entanglement length and one above. Under quiescent conditions,
we observe that entanglement does not have an effect on the nucleation
mechanism. For both chain lengths, the chains first align and then straighten
locally. Then the local density increases and finally positional ordering sets
in. At low shear rates the nucleation mechanism is the same as under quiescent
conditions, while at high shear rates the chains align and straighten at the
same time. We report on the effects of shear rate and temperature on the
nucleation rates and estimate the critical shear rates, beyond which the
nucleation rates increase with the shear rate. We show that the viscosity of
the system is not affected by the crystalline nuclei.Comment: 9 page
