75 research outputs found
Isotropic-nematic phase equilibria in the Onsager theory of hard rods with length polydispersity
We analyse the effect of a continuous spread of particle lengths on the phase
behavior of rodlike particles, using the Onsager theory of hard rods. Our aim
is to establish whether ``unusual'' effects such as isotropic-nematic-nematic
(I-N-N) phase separation can occur even for length distributions with a single
peak. We focus on the onset of I-N coexistence. For a log-normal distribution
we find that a finite upper cutoff on rod lengths is required to make this
problem well-posed. The cloud curve, which tracks the density at the onset of
I-N coexistence as a function of the width of the length distribution, exhibits
a kink; this demonstrates that the phase diagram must contain a three-phase
I-N-N region.
Theoretical analysis shows that in the limit of large cutoff the cloud point
density actually converges to zero, so that phase separation results at any
nonzero density; this conclusion applies to all length distributions with
fatter-than-exponentail tails. Finally we consider the case of a Schulz
distribution, with its exponential tail. Surprisingly, even here the long rods
(and hence the cutoff) can dominate the phase behaviour, and a kink in the
cloud curve and I-N-N coexistence again result. Theory establishes that there
is a nonzero threshold for the width of the length distribution above which
these long rod effects occur, and shows that the cloud and shadow curves
approach nonzero limits for large cutoff, both in good agreement with the
numerical results.Comment: 20 pages, 13 figure
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