Effects of polymer chain length and stiffness on phase separation dynamics of semidilute polymer solution.

Three-dimensional dissipative particle dynamics (DPD) simulations were performed to investigate the phase separation dynamics of semidilute polymer solutions with different polymer chain length and stiffness. For the polymer solution composed of shorter and more flexible chains, a crossover of the domain growth exponent from 1/3 to 2/3 was observed during the course of phase separation, indicating that the growth mechanism altered from diffusion to interfacial-tension driven flow. When the chain flexibility was kept the same but the chain was lengthened to allow for the chain entanglement to occur, the growth exponent changed to 1/4 in the diffusion-dominating coarsening regime while the growth exponent remained 2/3 in the flow-dominating regime. When the chain length was kept short but the stiffness was increased, the growth exponent became 1/6 in the diffusion-dominating regime and little effect was observed in the flow-dominating coarsening regime. The slow down of the phase separation dynamics in the diffusion-dominating coarsening could be explained by that the polymer chains could only perform wormlike movement when chain entanglements occurred or when the chain motion was limited by chain stiffness during phase separation. Moreover, when both the effects of chain length and stiffness were enhanced, polymer networks composed of longer and stiffer chains appeared and imposed an energy barrier for phase separation to occur. As a result, the polymer solution with stiffer and longer chains required a larger quench depth to initiate the phase separation and caused the delay in crossover of the coarsening mechanism from diffusion to flow.