arXiv subjects

Eric R. Dufresne

Publications and source records attributed to Eric R. Dufresne.

At least 19 recordsLinked to original sources

arXiv2026

Dispersion Polymerization in an Elastomeric Solvent

Polymerization-induced phase separation (PIPS) provides a powerful route to generate structured polymeric materials by coupling chemical conversion with thermodynamic demixing. PIPS in liquid-state systems underlies dispersion polymerization, serving as a cornerstone technique for microparticle production, yet is constrained by solvent compatibility and limited range of morphologies. Here, we establish an elastically mediated PIPS regime that bridges these two limits by conducting controlled polymerization within a deformable elastomeric network. This approach, termed Dispersion Polymerization in an Elastomeric Solvent (DiPolES), serves as a solid-state analogue of dispersion polymerization in which an elastomeric network simultaneously serves as solvent and physical stabilizer. Using photoiniferter-mediated polymerization of methyl methacrylate (MMA) within poly(dimethyl siloxane) (PDMS) elastomeric solvent, DiPolES enables robust fabrication of elastomeric composites containing uniform PMMA microparticles with tunable size (0.85 to 3 μm) and shape (spheroidal and ellipsoidal). The strategy is generalizable beyond the PDMS/MMA system and is applicable to diverse monomers, such as acrylonitrile and 2-vinyl pyridine, which can be extracted from the elastomeric solvent, enabling high-yield production of microparticles. Real-time imaging and compositional analysis reveal that particle formation proceeds through rapid nucleation at low monomer conversion, followed by growth accompanied by cavitation of the surrounding network. Monomer loading governs the particle size, while solvent elasticity modulates the transition from isolated uniform spheroids to heterogeneous clusters. Interestingly, applying uniaxial strain during DiPolES enables production of ellipsoidal particles without any post-processing.

cond-mat.soft↗

arXiv2026

Phase behavior of solvent-nematogen mixtures

Liquid mixtures with a nematogen can undergo both fluid phase separation and a transition from an isotropic to a nematic state. These phase transitions can couple and lead to phase behavior distinct from simple liquid mixtures or pure liquid crystals. We measured the phase behavior of mixtures of a nematogen (5CB) with simple liquid solvents (squalane and/or squalene). We observed two distinct kinds of binary phase diagrams: with and without a region of isotropic-isotropic coexistence. Varying the ratio of squalene to squalane, we continuously tuned the phase boundaries of the apparent binary system and revealed a region of three-phase coexistence. A mean-field model combining classical models of liquid mixing and nematic ordering quantitatively describes both binary and ternary phase behavior. This simple model predicts a range of topologically complex ternary phase diagrams and extends naturally to systems with more components.

cond-mat.soft↗

arXiv2026

Unravelling the multiscale surface mechanics of soft solids

Soft solids and their surface deformations control the response of many natural and artificial systems. Yet, their underlying properties are vigorously debated, particularly for polymer networks. While molecular-scale theories predict no interfacial changes with macroscopic deformation, multiple experiments suggest otherwise. To settle this issue, we measure displacement fields near the interface of a silicone gel, in the limit of small deformations. We discover an unexpected multiscale response. The shear modulus decreases smoothly by half with 20 microns of the interface. At the same time we observe a surface excess elasticity, that depends on history and outer medium composition. These results reveal the fundamentally multiscale nature of polymeric surfaces, and call for further experimental and theoretical investigations into the basic understanding of soft solid interfaces

cond-mat.soft↗

arXiv2025

Disordered origins, deterministic outcomes: How the architecture of elastic networks imprints relaxed structure and mechanics

This work targets the influence of disorder on the relaxed structure and macroscopic mechanical properties of elastic networks. We construct network classes of different types of disorder (length, topology and stiffness), which are subsequently equilibrated in a finite kinematics setting. Relaxed network structures are distinct among network classes, which opens the path towards exploiting easily accessible experimental measures as a way of inferring further microstructural details.

cond-mat.soft↗

arXiv2025

Controlling polymerization-induced phase separation in the synthesis of porous gels

Porous gels -- gels with solvent-filled pores that are much larger than their mesh size -- are widely used in engineering and biomedical applications due to their tunable mechanics, high water content, and selective permeability. Among various strategies to create porous gels, polymerization-induced phase separation (PIPS) has shown particular promise. However, the conditions that trigger and control PIPS remain poorly understood. Here, we systematically investigate the influence of solvent quality, polymeric precursor molecular weight, and polymer concentration on phase separation in polymerizing poly(ethylene glycol) diacrylate gels. We find that phase separation occurs when the precursor solution concentration is below the overlap concentration. Phase-separated gels have a pore geometry that is controlled by solvent quality: better solvents result in smaller pores, while worse solvents can create superporous, highly-absorbant gels. Motivated by our results, we propose a theory that predicts when phase separation occurs in polymerizing gels, applicable across a wide range of polymer/solvent gel systems. Our results provide a framework for the rational design of porous gels.

cond-mat.soft↗

arXiv2025

Could Living Cells Use Phase Transitions to Process Information?

To maintain homeostasis, living cells process information with networks of interacting molecules. Traditional models for cellular information processing have focused on networks of chemical reactions between molecules. Here, we describe how networks of physical interactions could contribute to the processing of information inside cells. In particular, we focus on the impact of biomolecular condensation, a structural phase transition found in cells. Biomolecular condensation has recently been implicated in diverse cellular processes. Some of these are essentially computational, including classification and control tasks. We place these findings in the broader context of physical computing, an emerging framework for describing how the native dynamics of nonlinear physical systems can be leveraged to perform complex computations. The synthesis of these ideas raises questions about expressivity (the range of problems that cellular phase transitions might be able to solve) and learning (how these systems could adapt and evolve to solve different problems). This emerging area of research presents diverse opportunities across molecular biophysics, soft matter, and physical computing.

physics.bio-ph↗

arXiv2025

Thermodynamics of microphase separation in a swollen, strain-stiffening polymer network

Elastic MicroPhase Separation (EMPS) provides a simple route to create soft materials with homogeneous microstructures by leveraging the supersaturation of crosslinked polymer networks with liquids. At low supersaturation, network elasticity stabilizes a uniform mixture, but beyond a critical threshold, metastable microphase-separated domains emerge. While previous theories have focused on describing qualitative features about the size and morphology of these domains, they do not make quantitative predictions about EMPS phase diagrams. In this work, we extend Flory-Huggins theory to quantitatively capture EMPS phase diagrams by incorporating strain-stiffening effects. This model requires no fitting parameters and relies solely on independently measured solubility parameters and large-deformation mechanical responses. Our results reveal that strain-stiffening enables metastable microphase separation within the swelling equilibrium state and why the microstructures can range from discrete droplets to bicontinuous networks. This works highlights the critical role of nonlinear elasticity in controlling phase-separated morphologies in polymer gels.

cond-mat.soft↗

arXiv2024

Droplets sliding on soft solids shed elastocapillary rails

The surface tension of partially wetting droplets deforms soft substrates. These deformations are usually localized to a narrow region near the contact line, forming a so-called `elastocapillary ridge.' When a droplet slides along a substrate, the movement of the elastocapillary ridge dissipates energy in the substrate and slows the droplet down. Previous studies have analyzed isotropically spreading droplets and found that the advancing contact line `surfs' the elastocapillary ridge, with a velocity determined by a local balance of capillary forces and bulk rheology. Here, we experimentally explore the dynamics of a droplet sliding across soft substrates. At low velocities, the contact line is nearly circular, and dissipation increases logarithmically with speed. At higher droplet velocities, the contact line adopts a bullet-like shape, and the dissipation levels off. At the same time, droplets shed a pair of `elastocapillary rails' that fade away slowly behind it. These results suggest that droplets favor sliding along a stationary ridge over surfing atop a translating one.

cond-mat.soft↗

arXiv2024

Characterizing hydrogel behavior under compression with gel-freezing osmometry

Hydrogels are particularly versatile materials that are widely found in both Nature and industry. One key reason for this versatility is their high water content, which lets them dramatically change their volume and many of their mechanical properties -- often by orders of magnitude -- as they swell and dry out. Currently, we lack techniques that can precisely characterize how these properties change with water content. To overcome this challenge, here we develop Gel-Freezing Osmometry (GelFrO): an extension of freezing-point osmometry. We show how GelFrO can measure a hydrogel's mechanical response to compression and osmotic pressure, while only using small, $O(100μ$L$)$ samples. Because the technique allows measurement of properties over an unusually wide range of water contents, it allows us to accurately test theoretical predictions. We find simple, power-law behavior for both mechanical response to compression, and osmotic pressure, while these are not well-captured by classical Flory-Huggins theory. We interpret this power-law behavior as a hallmark of a microscopic fractal structure of the gel's polymer network, and propose a simple way to connect the gel's fractal dimension to its mechanical and osmotic properties. This connection is supported by observations of hydrogel microstructures using small-angle x-ray scattering. Finally, our results motivate us to propose an updated constitutive model describing hydrogel swelling, and mechanical response.

cond-mat.soft↗

arXiv2024

Liquid-liquid phase separation of proteins is modulated by amino acids in vitro and in vivo by regulating protein-protein interactions

Liquid liquid phase separation (LLPS) of proteins is an intracellular process that is widely used by cells for many purposes. In living cells (in vivo), LLPS occurs in complex and crowded environments. Amino acids (AAs) are vital components of such environments, occupying a significant fraction of the cellular volume. In this work, we studied the effects of proline and other proteinogenic AAs on the LLPS of proteins, both in test tubes (in vitro) and in cells (in vivo). The effects of proline on the protein-protein interaction (PPI) and LLPS of both bovine serum albumin (BSA, a folded protein) and the low-complexity domain of fused in sarcoma (FUS267, an intrinsically disordered protein) is first established in vitro. Then, the effects of proline and other proteinogenic AAs on the formation of stress granules (SGs) by LLPS in U2OS and HeLa cells are studied. We find that the presence of AAs renders the net interaction between proteins more repulsive (i.e. stabilizes protein solution), thus suppressing protein phase separation in vitro and in vivo. We also show that the formation of SGs is suppressed by AAs using both immunofluorescence and live-cell microscopy. Our study reveals an underappreciated role of cellular AAs in modulating intracellular phase separation. It may find biomedical applications, especially in the treatment of protein aggregation diseases.

physics.bio-ph↗

arXiv2024

Dehydration drives damage in the freezing of brittle hydrogels

It is widely known that freezing breaks soft, wet materials. However, the mechanism underlying this damage is still not clear. To understand this process, we freeze model, brittle hydrogel samples, while observing the growth of ice-filled cracks that break these apart. We show that damage is not caused by the expansion of water upon freezing, or the growth of ice-filled cavities in the hydrogel. Instead, local ice growth dehydrates the surrounding hydrogel, leading to drying-induced fracture. This dehydration is driven by the process of cryosuction, whereby undercooled ice sucks nearby water towards itself, feeding its growth. Our results highlight the strong analogy between freezing damage and desiccation cracking, which we anticipate being useful for developing an understanding of both topics. Our results should also give useful insights into a wide range of freezing processes, including cryopreservation, food science and frost heave.

cond-mat.soft↗

arXiv2023

Polycrystallinity enhances stress build-up around ice

Damage caused by freezing wet, porous materials is a widespread problem, but is hard to predict or control. Here, we show that polycrystallinity makes a great difference to the stress build-up process that underpins this damage. Unfrozen water in grain-boundary grooves feeds ice growth at temperatures below the freezing temperature, leading to the fast build-up of localized stresses. The process is very variable, which we ascribe to local differences in ice-grain orientation, and to the surprising mobility of many grooves -- which further accelerates stress build-up. Our work will help understand how freezing damage occurs, and in developing accurate models and effective damage-mitigation strategies.

cond-mat.soft↗

arXiv2023

Phase separation dependent active motion of Janus lipid vesicles

Active colloidal systems have emerged as promising contenders for the future of microdevices. While conventional designs have extensively exploited the use of hard colloids, the advancement of cell-inspired architectures represents a pivotal path towards realizing self-regulating and highly functional artificial microswimmers. In this work, we fabricate and actuate Janus lipid vesicles demonstrating reconfigurable motion under an AC electric field. The giant unilamellar vesicles (GUVs) undergo spontaneous phase separation at room temperature leading to Janus-like GUVs with two distinct lipid phases. We report self-propulsion of the Janus GUVs via induced charge electroosmosis, in between parallel electrodes. Remarkably, the fluid nature of the lipid membrane affected by the electric field leads to asymmetry-symmetry transient states resulting in run-and-tumble events supported by structure domain analysis. We characterise an enhanced rotational diffusivity associated with tumble events, decoupled from thermal reorientation. Lastly, we identify cargo-release capabilities and a variety of shape-encoded dynamic modes in these vesicles. This cell-inspired architecture provides an alternative route for creating motile artificial cells and programmable microswimmers.

cond-mat.soft↗

arXiv2023

Efficient structural color from pigment-loaded nanostructures

Color can originate from wavelength-dependence in the absorption of pigments or the scattering of nanostructures. While synthetic colors are dominated by the former, vivid structural colors found in nature have inspired much research on the latter. However, many of the most vibrant colors in nature involve the interactions of structure and pigment. Here, we demonstrate that pigment can be exploited to efficiently create bright structural color at wavelengths outside its absorption band. We created pigment-enhanced Bragg reflectors by sequentially spin-coating layers of poly-vinyl alcohol (PVA) and polystyrene (PS) loaded with $β$-carotene (BC). With only 10 double layers, we acheived a peak reflectance over $0.8$ at 550 nm and normal incidence. A pigment-free multilayer made of the same materials would require 25 double layers to achieve the same reflectance. Further, pigment loading suppressed the Bragg reflector's characteristic iridescence. Using numerical simulations, we further show that similar pigment loadings could significantly expand the gamut of non-iridescent colors addressable by photonic glasses.

cond-mat.soft↗

arXiv2023

Strain-stiffening elastomers fail from the edge

The accurate measurement of fracture resistance in elastomers is essential for predicting the mechanical limits of soft devices. Usually, this is achieved by performing tearing or peeling experiments on thin-sheet samples. Here, we show that these tests can be surprisingly thickness-dependent, with thicker samples being significantly stronger than thinner ones. Even for a simple geometry, direct imaging of the fracture surface shows that the fracture process actually involves three distinct cracks: an inner crack, and two edge cracks. Ultimately, samples fail when two edge cracks meet at the sample's mid-plane. The opening angle of edge crack, $2 θ$, determines how far the sample has to be stretched before the edge cracks meet. Conveniently, $θ$ is a material property that can be inferred from the elastomer's non-linear elastic response. To yield thickness-independent fracture-test results, sample thickness should be much smaller than the smallest lateral sample dimension divided by $\tan θ$. Our results have direct implications for characterizing, understanding, and modelling fracture in soft elastomers.

cond-mat.soft↗

arXiv2023

Surface Passivation Method for Super-repellence of Aqueous Macromolecular Condensates

Solutions of macromolecules can undergo liquid-liquid phase separation to form droplets with ultra-low surface tension. Droplets with such low surface tension wet and spread over common surfaces such as test tubes and microscope slides, complicating \textit{in vitro} experiments. Development of an universal super-repellent surface for macromolecular droplets has remained elusive because their ultra-low surface tension requires low surface energies. Furthermore, nonwetting of droplets containing proteins poses additional challenges because the surface must remain inert to a wide range of chemistries presented by the various amino-acid side-chains at the droplet surface. Here, we present a method to coat microscope slides with a thin transparent hydrogel that exhibits complete dewetting (contact angles $θ\approx180^\circ)$ and minimal pinning of phase-separated droplets in aqueous solution. The hydrogel is based on a swollen matrix of chemically crosslinked polyethylene glycol diacrylate of molecular weight 12 kDa (PEGDA), and can be prepared with basic chemistry lab equipment. The PEGDA hydrogel is a powerful tool for \textit{in vitro} studies of weak interactions, dynamics, and internal organization of phase-separated droplets in aqueous solutions.

cond-mat.soft↗

arXiv2023

Elastic Microphase Separation Produces Robust Bicontinuous Materials

Bicontinuous microstructures are essential to the function of diverse natural and synthetic systems. Their synthesis has been based on two approaches: arrested phase separation or self-assembly of block copolymers. The former is attractive for its chemical simplicity, the latter for its thermodynamic robustness. Here, we introduce Elastic MicroPhase Separation (EMPS) as an alternative approach to make bicontinuous microstructures. Conceptually, EMPS balances the molecular-scale forces that drive demixing with large-scale elasticity to encode a thermodynamic length scale. This process features a continuous phase transition, reversible without hysteresis. Practically, we trigger EMPS by simply super-saturating an elastomeric matrix with a liquid. This results in uniform bicontinuous materials with a well-defined microscopic length-scale tuned by the matrix stiffness. The versatility and robustness of EMPS is further demonstrated by fabricating bicontinuous materials with superior mechanical properties and controlled anisotropy and microstructural gradients.

cond-mat.soft↗

arXiv2023

Siloxane molecules: Nonlinear elastic behavior and fracture characteristics

Fracture phenomena in soft materials span multiple length- and timescales. This poses a major challenge in computational modeling and predictive materials design. To pass quantitatively from molecular- to continuum scales, a precise representation of the material response at the molecular level is vital. Here, we derive the nonlinear elastic response and fracture characteristics of individual siloxane molecules using molecular dynamics (MD) studies. For short chains, we find deviations from classical scalings for both the effective stiffness and mean chain rupture times. A simple model of a non-uniform chain of Kuhn segments captures the observed effect and agrees well with MD data. We find that the dominating fracture mechanism depends on the applied force scale in a non-monotonic fashion. This analysis suggests that common polydimethylsiloxane (PDMS) networks fail at crosslinking points. Our results can be readily lumped into coarse-grained models. Although focusing on PDMS as a model system, our study presents a general procedure to pass beyond the window of accessible rupture times in MD studies employing mean first passage time theory, which can be exploited for arbitrary molecular systems.

cond-mat.soft↗