Search arXiv⌕ Search
Home/Archive/arXiv

arXiv · 2111.08055

Chain Conformations and Phase Separation in Polymer Solutions with Varying Solvent Quality

Yisheng Huang·Shengfeng Cheng
View original source ↗Read source document ↗Export metadata ↓

Abstract

Molecular dynamics simulations are used to investigate the conformations of a single polymer chain, represented by the Kremer-Grest bead-spring model, in a solution with a Lennard-Jones liquid as the solvent when the interaction strength between the polymer and solvent is varied. Results show that when the polymer-solvent interaction is unfavorable, the chain collapses as one would expect in a poor solvent. For more attractive polymer-solvent interactions, the solvent quality improves and the chain is increasingly solvated and exhibits ideal and then swollen conformations. However, as the polymer-solvent interaction strength is increased further to be more than about twice of the strength of the polymer-polymer and solvent-solvent interactions, the chain exhibits an unexpected collapsing behavior. Correspondingly, for strong polymer-solvent attractions, phase separation is observed in the solutions of multiple chains. These results indicate that the solvent becomes effectively poor again with very attractive polymer-solvent interactions. Nonetheless, the mechanism of chain collapsing and phase separation in this limit differs from the case with a poor solvent rendered by unfavorable polymer-solvent interactions. In the latter, the solvent is excluded from the domain of the collapsed chains while in the former, the solvent is still present in the pervaded volume of a collapsed chain or in the polymer-rich domain that phase separates from the pure solvent. In the limit of strong polymer-solvent attractions, the solvent behaves as a glue to stick monomers together, causing a single chain to collapse and multiple chains to aggregate and phase separate.

Explore related subjects

cond-mat.soft

Keep this discovery

Explore connections, maps & timelines

BibTeXRIS

Yisheng Huang, Shengfeng Cheng. 2021-11-15. Chain Conformations and Phase Separation in Polymer Solutions with Varying Solvent Quality. https://doi.org/10.1002/pol.20210526

Cite the original work for its findings. Save a collection to share your selection of sources.

KEEP EXPLORING

Related papers

arXiv2026

Transient Elasticity -- A Unifying Framework for Thixotropy, Polymers, and Granular Media

Thixotropic yield stress fluids, such as paint or ketchup, are traditionally viewed as elastic structures that, under shear rates, break into viscous liquids with lumps, and reconnect at rest. An alternative framework is presented here: Upon shear, structural destruction is incomplete, leaving sufficient connections. As a result, elasticity fundamentally underlies their non-Newtonian behavior, though they do appear purely viscous under a steady shear, displaying little direct evidence of elastic rebound---same as granular media and polymers. Consequently, all three are described by the same set of evolution equations, differing only in their parameters. These equations are set up by starting from solid dynamics and allowing the elastic strain $\varepsilon^e$ to relax, which in effect interpolates between solid and fluid behavior, appropriate for systems that display both types of behavior. Incorporating in addition a two-temperature framework, tracking how energy is dissipated in two consecutive stages, yields the nonlinear model of Transient Elasticity (TE). It describes an elasticity that is transient in time yet persistent under shear. Previously validated for polymers and granular media, TE is here applied to thixotropic yield-stress fluids. As shown, it successfully accounts for a wide range of characteristic phenomena, including over- and undershoot, viscosity bifurcation, shear banding, and oscillatory rheography. Given its appropriateness across structurally diverse systems, TE offers a unified, surprisingly general account of non-Newtonian phenomena.

cond-mat.soft↗
arXiv2026

Deformation and organization of droplet-encapsulated soft beads

Many biological, culinary, and engineering processes lead to the co-encapsulation of several soft particles within a liquid interface. In these situations the particles are bound together by the capillary forces that deform them and influence their biological or rheological properties. Here, we introduce an experimental approach to encapsulate a controlled number of soft beads within aqueous droplets in oil. These droplet-encapsulated gels are manipulated in a deformable microfluidic device to merge them and modify the liquid fraction. In the dry limit the contact surface between the hydrogels is found to be determined by the elastocapillary number $E_c$, with the contact radius following a $E_c^{1/3}$ dependence, indicating that the deformation increases for soft or small particles. When multiple beads are co-encapsulated within a single droplet they can be arranged into linear or three-dimensional aggregates that remain at a local energy minimum.

cond-mat.soft↗
arXiv2026

Flexoelectricity-driven softening of bend elasticity leads to spontaneous chiral symmetry breaking in a polar fluid

The origin of the recently observed spontaneous chiral symmetry breaking in polar fluids composed of achiral molecules is an unsolved problem, raising fundamental questions about how heliconical structures emerge in such systems. Here, we investigate the pretransitional fluctuations leading to the formation of the spontaneously chiral twist-bend ferroelectric nematic phase using dielectric spectroscopy, light scattering, and small-angle X-ray scattering. We observe simultaneous softening of the bend elastic constant and the emergence of a collective dielectric mode on approaching the transition. By developing a theoretical model, we show that these phenomena are signatures of a flexoelectricity-driven transition arising from the coupling between electric polarization and bend deformation.

cond-mat.soft↗