Megasupramolecules for safer, cleaner fuel by end association of long telechelic polymers.

We used statistical mechanics to design polymers that defy conventional wisdom by self-assembling into "megasupramolecules" (≥5000 kg/mol) at low concentration (≤0.3 weight percent). Theoretical treatment of the distribution of individual subunits­end-functional polymers­among cyclic and linear supramolecules (ring-chain equilibrium) predicts that megasupramolecules can form at low total polymer concentration if, and only if, the backbones are long (>400 kg/mol) and end-association strength is optimal. Viscometry and scattering measurements of long telechelic polymers having polycyclooctadiene backbones and acid or amine end groups verify the formation of megasupramolecules. They control misting and reduce drag in the same manner as ultralong covalent polymers. With individual building blocks short enough to avoid hydrodynamic chain scission (weight-average molecular weights of 400 to 1000 kg/mol) and reversible linkages that protect covalent bonds, these megasupramolecules overcome the obstacles of shear degradation and engine incompatibility.

Theoretical analysis on the refractive-index distribution and bandwidth of gradient-index polymer optical fibers from a centrifugal field.

Theoretical analysis was applied to analyze the refractive-index distribution (RID) and bandwidth (BW) of gradient-index polymer optical fibers (GI POFs) prepared by a centrifugal field process. The RID of the prepared GI POF could be represented by the equation of n(r) = n1[1 - 2delta(r/alpha)g](1/2). The studied material systems were poly(hexafluoroisopropyl 2-fluoroacrylate) (PHFIP 2-FA)/dibutyl phthalate (DBP) and poly(methyl methacrylate) (PMMA)/benzyl benzoate (BEN). The RID and the BW were significantly affected by an essential parameter k, which was related to thematerial properties (density difference and molecular weight) and processing properties (rotating speed, temperature, and radius). As k increased, the characteristic constant of RID, g, decreased to a minimum and then increased sharply, owing to the separation of the polymer and the dopant. On the other hand, the relative refractive-index difference of RID, delta, increased to a steady value after k increased to a certain value. The variation of RID with k resulted in a local minimum of intermodal dispersion, and thus a maximum bandwidth was obtained. The maximum BW of the PHFIP 2-FA/DBP and PMMA/BEN systems at 1550 nm (100-m fiber length and 2-nm spectral width) for the case of k not equal to 0 were 6.7 and 3.2 Gb/s, respectively. The wavelength of light source affects the BW significantly only at k around zero because of the importance of the intramodal dispersion in this case.