Theoretical issues relating to thermally reversible gelation by supermolecular fiber formation

Existing models of the thermodynamics and dynamics of self-assembly are summarized to provide a context for discussing the difficulties that arise in modeling supermolecular fiber assembly and the formation of thermally reversible gels through fiber growth and branching. Challenging problems in this field, such as the physical origin of fibers of uniform diameter and fiber twisting, the kinetics of fiber growth, the hierarchical bundling of fibers into "superfibers", fiber branching, gelation through fiber impingement and the associated phenomenon of fractal fiber network and spherulite formation, and the origin and control of structural polymorphism in the fiber and superfiber geometry, are discussed from a personal perspective. Suggestions are made for integrating current research efforts into a more coherent multiscale description of fiber formation and gelation on molecular, mesoscopic, and macroscopic scales.