ORDERED STRUCTURE IN BLOCK POLYMER-SOLUTIONS .6. POSSIBLE NONEQUILIBRIUM EFFECTS ON GROWTH OF SELF-ASSEMBLING STRUCTURES

We explore non-equilibrium effects on the growth of microdomain structures in block polymer solutions with a neutrally good solvent. The growth of microdomain structures induced by increasing segregation power with increase of polymer concentration øp is hindered by morphology-dependent non-equilibrium effects. For spherical microdomains with discontinuous interfaces, the effects set in when the change in number of block chains per domain cannot follow the change of øp. For other types of microdomains with continuous interfaces, such as cylindrical, bicontinuous and lamellar microdomains, the effects set in when the average separation of chemical junctions of block polymer chains along the interface cannot follow the change of øp. The effects for spheres are primarily caused by 'suppressed mutual diffusivity' of the block chains from one sphere to others with increasing øp. The effects for other morphologies are caused by 'grain-boundary effects' discussed in the text and/or vitrification of one type of domain. In the case when changes of the states of the system are sufficiently slow, vitrification becomes the primary cause of the non-equilibrium phenomena, regardless of the morphology of the solution. © 1990.