Predicting the phase behavior of ABAC tetrablock terpolymers: Sensitivity to Flory–Huggins interaction parameters

• Published in: Polymer (Guilford) Vol. 154; pp. 305 - 314
• Main Authors: Arora, Akash, Pillai, Naveen, Bates, Frank S., Dorfman, Kevin D.
• Format: Journal Article
• Language: English
• Published: Kidlington Elsevier Ltd 10.10.2018; Elsevier BV
• Subjects: Block polymer; Computer simulation; Ethylene; Ethylene oxide; Flory-Huggins theory; Free energy; Interaction parameters; Isoprene; Mathematical models; Mean field theory; Molecular dynamics; Nanostructured materials; Order-disorder transformations; Organic chemistry; Parameter estimation; Parameter sensitivity; Phase behavior; Polyethylene; Polyethylene oxide; Polymers; Polystyrene resins; Predictions; Self-consistent field theory; Sensitivity; Structure factor; Styrene; Styrenes; Terpolymers; Thermodynamics; Transition temperature; Transition temperatures; Self-consistent field theory; Block polymer; Phase behavior; Flory-Huggins theory
• ISSN: 0032-3861; 1873-2291
• DOI: 10.1016/j.polymer.2018.08.070

Self-consistent field theory (SCFT) is a powerful tool for discovering new nanostructures in self-assembling block polymers. However, the reliability of the resulting predictions depend strongly on the Flory-Huggins interaction parameters χij used to quantify the excess free energy of mixing of different blocks i and j arising from segment-segment interactions. The problem is especially significant for multiblock polymers, owing to the multitude of χij parameters and the sensitivity of the resulting phase behavior when the χij do not differ substantially for different block pairs. To illuminate this issue, we examine how the SCFT-predicted phase behavior of a poly(styrene)-b-poly(isoprene)-b-poly(styrene)'-b-poly(ethylene oxide) (SIS'O) tetrablock terpolymer changes depending on the method used to estimate the trio of χij parameters for this chemistry. SIS'O is an ideal model system for our purposes, as it exhibits a large number of poly(ethylene oxide) sphere-forming phases, emerging from the segregation of the poly(ethylene oxide) block due to the relatively high values of χSO and χIO, accompanied by subtle matrix segregation effects arising due to the smaller χIS between poly(isoprene) and poly(styrene). We first use χIS, χIO, and χSO available in the literature that were estimated using mean-field theory order–disorder transitions of the relevant diblock polymers. As this method is expected to lead to significant errors in χij that propagate into the SCFT predictions, we also consider two fluctuation-corrected approaches to extract χij from diblock polymer data, namely (i) fitting the order-disorder transition temperature to that predicted by molecular dynamics simulations and (ii) renormalized one-loop theory predictions for the structure factor of the disordered state. While even the fluctuation-corrected χ parameters do not lead to SCFT phase behavior that exactly matches experiments, the SCFT calculations using the molecular dynamics-fitted χ parameters correctly predict stable Frank–Kasper A15 and σ phases. The results presented here highlight the challenges in predictively modeling the phase behavior of multiblock polymers using SCFT, a critical task for the discovery of new multiblock polymer materials. [Display omitted] •Comparison of the Flory-Huggins χ-parameters for three diblock polymers using three different methods.•Demonstration that these different methods lead to qualitatively different self-consistent field theory phase diagrams.•None of these methods predicts the complete sequence of phase transitions observed in experiments.•The simulation-based χ-parameters correctly predict stable Frank-Kasper A15 and σ phases.•Provides a cautionary example for the use of SCFT to predict the phase behavior of multiblock polymers.