Kinetics of phase transitions in weakly segregated block copolymers: Pseudostable and transient states

We study the kinetics of order-disorder and order-order transitions in weakly segregated diblock copolymers using a time-dependent Ginzburg-Landau (TDGL) approach. In particular, we investigate the microstructural change as well as the order-parameter evolution after a sudden temperature jump from one phase to another. Direct numerical simulation of the TDGL equations shows that depending on the extent of the temperature jump, these transitions often occur in several stages and can involve nontrivial intermediate states. For example, we find that transition from the lamellar phase to the hexagonal cylinder phase goes through a perforated lamellar state within a certain temperature range. The numerical results are elucidated by a multimode analysis under the single-wave-number approximation. The analysis reveals that the geometric characteristics of the free energy surface, particularly saddle points and ridgelike features, are responsible for the nontrivial intermediate states on the kinetic pathways. On the basis of this analysis, a generalized kinetic ''phase diagram'' is constructed, which is able to account for all the different scenarios observed in the numerical simulation. Our results are discussed in connection with available experimental observations. In particular, we suggest the possibility that the perforated-modulated lamellar structures obtained by Bales and co-workers [I. W. Hamley, K. A. Koppi, J. H. Rosedale, F. S. Bates, K. Almdal, and K. Mortensen, Macromolecules 26, 5959 (1993); S. Forster, A. K. Khandpur, J. Zhao, F. S. Bates, I. W. Hamley, A. J. Ryan, and W. Bras, Macromolecules 27, 6922 (1994)] may be kinetic, intermediate states rather than new equilibrium phases.