arXiv subjects

Rajam Elancheliyan

Publications and source records attributed to Rajam Elancheliyan.

3 recordsLinked to original sources

arXiv2026

Universal scalings and switching entropy in yield-stress fluids

Yield-stress fluids transition from solid-like to liquid-like behavior at a critical stress threshold, governing phenomena from industrial processing to geological flows. While predominantly investigated under steady shear, large-amplitude oscillatory tests force these materials to cyclically navigate between arrested and fluidized states. Here, we discover a hidden universal behavior where the dynamic viscoelastic moduli of yield-stress fluids collapse onto master curves, revealing that these materials rearrange almost instantaneously to maintain a constant intra-cycle stress state. We fully capture this behavior using a novel theoretical framework based on the minimization of a governing function that exhibits symmetry breaking. Our findings reveal that recoverable elastic energy, yielding abruptness, and entropy production during stress inversion are fundamentally intertwined. This connection provides a unified physical picture for the dynamic yield stress, offering a novel thermomechanical foundation to define and predict this threshold across soft matter physics and materials science.

cond-mat.soft↗

arXiv2023

Impact of polyelectrolyte adsorption on the rheology of concentrated Poly(N-Isopropylacrylamide) microgel suspensions

We explore the impact of three water-soluble polyelectrolytes (PEs) on the flow of concentrated suspensions of poly(N-isopropylacrylamide) (PNIPAm) microgels with thermoresponsive anionic charge density. By progressively adding the PEs to a jammed suspension of swollen microgels, we show that the rheology of the mixtures is remarkably influenced by the sign of the PE charge, PE concentration and hydrophobicity only when the temperature is raised above the microgel volume phase transition temperature $T_c$, namely when microgels collapse, they are partially hydrophobic and form a volume-spanning colloidal gel. We find that the original gel is strengthened close to the isoelectric point, attained when microgels are mixed with cationic PEs, while PE hydrophobicity rules the gel strengthening at very high PE concentrations. Surprisingly, we find that polyelectrolyte adsorption or partial embedding of PE chains inside the microgel periphery occurs also when anionic polymers of polystyrene sulfonate with high degree of sulfonation are added. This gives rise to colloidal stabilization and to the melting of the original gel network above $T_c$. Contrastingly, the presence of polyelectrolytes in suspensions of swollen, jammed microgels results in a weak softening of the original repulsive glass, even when an apparent isoelectric condition is met. Our study puts forward the crucial role of electrostatics in thermosensitive microgels, unveiling an exciting new way to tailor the flow of these soft colloids and highlighting a largely unexplored path to engineer soft colloidal mixtures.

cond-mat.soft↗

arXiv2022

The role of charge content in the two-step deswelling of Poly(N-isopropylacrylamide)-based microgels

Poly(N-isopropylacrylamide)-based microgels are soft colloids undergoing a Volume Phase Transition (VPT) close to ambient temperature. Although widely employed for fundamental research and application purposes, the modifications of the microgel internal structure occurring at the VPT are not yet completely understood, especially concerning the role of electrostatics. Here we study in detail, both experimentally and numerically, the effect of the addition of acrylic acid (AAc) co-monomer on the microgel deswelling process. By combining viscosimetry, light scattering and electrophoresis, we show that the progressive addition of AAc increases the microgel mass and suppresses the occurrence of the VPT, progressively shifting the microgel collapse to higher temperatures. Most importantly, it also highly enhances the two-step deswelling of these submicron-sized networks, so that the inner core collapses at temperatures always lower than those marking the transition of the outer corona. These results indicate that a net increase of the charge density mismatch between the bulk and the surface of the microgels takes place. Numerical simulations fully confirm this scenario and clarify the impact of the charge distribution on the two-step deswelling, with mobile counterions efficiently screening the charges within the inner core, while leaving more monomers ionized on the surface. Our work unambiguously shows how electrostatic interactions influence the behavior of thermosensitive microgels in aqueous environment close to the VPT.

cond-mat.soft↗