A comparative study of force fields for predicting shape memory properties of liquid crystalline elastomers using molecular dynamic simulations

Molecular dynamic (MD) simulation techniques are increasingly being adopted as efficient computational tools to design novel and exotic classes of materials for which traditional methods of synthesis and prototyping are either too costly, unsafe, and time-consuming in laboratory settings. Of such class of materials are liquid crystalline elastomers (LCEs) with favorable shape memory characteristics. These materials exhibit some distinct properties, including stimuli responsiveness to heat or UV and appropriate molecular structure for shape memory behaviors. In this work, the MD simulations were employed to compare and assess the leading force fields currently available for modeling the behavior of a typical LCE system. Three force fields, including Dreiding, PCFF, and SciPCFF, were separately assigned to model the LCE system, and their suitability was validated through experimental results. Among these selected force fields, the SciPCFF produced the best agreement with the experimentally measured thermal and viscoelastic properties compared to those of simulated steady-state density, transition temperature, and viscoelastic characteristics. Next, shape fixity (Rf) and shape recovery (Rr) of LCEs were estimated using this force field. A four-step simulated shape memory procedure proceeded under a tensile mode. The changes in molecular conformations were calculated for Rf and Rr after the unloading step and the reheating step. The results revealed that the model LCE system exhibits characteristic behaviors of Rf and Rr over the thermomechanical shape memory process, confirming the suitability of selected force field for use in the design and prediction of properties of typical LCE class of polymers.