Simulation and theory of self-assembly and network formation in reversibly cross-linked equilibrium polymers

@article{kindt05a, abstract = {A simulation model of hard spheres capable of reversible assembly into chains, which then may reversibly cross-link into networks, has been studied through grand canonical Monte Carlo simulation. Effects of varying intra- and interchain bond strengths, chain flexibilities, and restrictions on cross-linking angle were investigated. Observations including chain-length distributions and phase separation could be captured in most cases using a simple model theory. The coupling of chain growth to cross-linking was shown to be highly sensitive to the treatment of cross-linking by chain ends. In some systems, ladderlike domains of several cross-links joining two chains were common, resulting from cooperativity in the cross-linking. Extended to account for this phenomenon, the model theory predicts that such cooperativity will suppress phase separation in weakly polymerizing chains and at high cross-link concentration. In the present model, cross-linking stabilizes the isotropic phase with respect to the nematic phase, causing a shift in the isotropic-nematic transition to higher monomer concentration than in simple equilibrium polymers. {\copyright}2005 American Institute of Physics}, author = {Kindt, James T. }, citeulike-article-id = {1790191}, doi = {http://dx.doi.org/10.1063/1.2046629}, journal = {The Journal of Chemical Physics}, keywords = {polymer-gel, simulation}, number = {14}, posted-at = {2007-10-19 19:58:34}, priority = {2}, publisher = {AIP}, title = {Simulation and theory of self-assembly and network formation in reversibly cross-linked equilibrium polymers}, url = {http://dx.doi.org/10.1063/1.2046629}, volume = {123}, year = {2005} }

TY - JOUR ID - kindt05a L3 - citeulike-article-id:1790191 TI - Simulation and theory of self-assembly and network formation in reversibly cross-linked equilibrium polymers JF - The Journal of Chemical Physics VL - 123 IS - 14 PB - AIP N2 - A simulation model of hard spheres capable of reversible assembly into chains, which then may reversibly cross-link into networks, has been studied through grand canonical Monte Carlo simulation. Effects of varying intra- and interchain bond strengths, chain flexibilities, and restrictions on cross-linking angle were investigated. Observations including chain-length distributions and phase separation could be captured in most cases using a simple model theory. The coupling of chain growth to cross-linking was shown to be highly sensitive to the treatment of cross-linking by chain ends. In some systems, ladderlike domains of several cross-links joining two chains were common, resulting from cooperativity in the cross-linking. Extended to account for this phenomenon, the model theory predicts that such cooperativity will suppress phase separation in weakly polymerizing chains and at high cross-link concentration. In the present model, cross-linking stabilizes the isotropic phase with respect to the nematic phase, causing a shift in the isotropic-nematic transition to higher monomer concentration than in simple equilibrium polymers. ©2005 American Institute of Physics KW - polymer-gel KW - simulation AU - Kindt, James PY - 2005/// UR - http://dx.doi.org/10.1063/1.2046629 ER -