Ed. Vonmeerwall et al., SORPTION KINETICS OF POLY(DIMETHYLSILOXANE) NETWORKS - DIFFUSION OF POLYDISPERSE PDMS BLENDS, Macromolecules, 31(3), 1998, pp. 669-674
Using the pulsed-gradient spin-echo NMR method, we have studied the di
ffusivity D of two highly polydisperse OH terminated dimethylsiloxane
blends (M-n = 15 900 and 26 400) in the melts and sorbed into networks
made by linking the same material with tetraethoxysilane; the sol was
carefully extracted before diffusant was added. Sorption took either
3 days for a 5% weight gain or 60 days for material weighing 5% of the
network to be completely absorbed; samples were then equilibrated. Fi
tting an echo attenuation model based on M distribution to the data sh
ows that for both systems the diffusion in the 3-day sample is several
times faster and more broadly distributed than in either its melt or
the 60-day sample, reflecting the tendency for smaller molecules to be
sorbed more rapidly. This finding complements our earlier similar fin
ding for sol extraction. The D distributions in the 60-day samples are
identical in shape, but slightly lower in mean rate, to those in the
neat melts, and both in excellent correspondence with the original M d
istributions, showing that the observed permselectivity is satisfactor
ily explained on the basis of sorption kinetics alone.