arXiv subjects

Eric R. Dufresne

Publications and source records attributed to Eric R. Dufresne.

At least 37 records · Page 2Linked to original sources

arXiv2023

The generalized Clapeyron equation and its application to confined ice growth

Most theoretical descriptions of stresses induced by freezing are rooted in the (generalized) Clapeyron equation, which predicts the pressure that a solid can exert as it cools below its melting temperature. This equation is central for topics ranging beyond glaciology to geomorphology, civil engineering, food storage, and cryopreservation. However, it has inherent limitations, requiring isotropic solid stresses and conditions near bulk equilibrium. Here, we examine when the Clapeyron equation is applicable by providing a rigorous derivation that details all assumptions. We demonstrate the natural extension for anisotropic stress states, and we show how the temperature and pressure ranges for validity depend on well-defined material properties. Finally, we demonstrate how the range of applicability of the (linear) Clapeyron equation can be extended by adding higher-order terms, yielding results that are in good agreement with experimental data for the pressure melting of ice.

cond-mat.soft↗

arXiv2022

ATRP enhances structural correlations in polymerization-induced phase separation

Synthetic methods to control the structure of materials at sub-micron scales are typically based on the self-assembly of structural building blocks with precise size and morphology. On the other hand, many living systems can generate structure across a broad range of length scales in one step directly from macromolecules, using phase separation. Here, we introduce and control structure at the nano- and microscales through polymerization in the solid state, which has the unusual capability of both triggering and arresting phase separation. In particular, we show that atom transfer radical polymerization (ATRP) enables control of nucleation, growth, and stabilization of phase-separated poly-methylmethacrylate (PMMA) domains in a solid polystyrene (PS) matrix. ATRP yields durable nanostructures with low size dispersity and high degrees of structural correlations. Furthermore, we demonstrate that the length scale of these materials is controlled by the synthesis parameters.

cond-mat.mtrl-sci↗

arXiv2022

Gradients in solid surface tension drive Marangoni-like motions in cell aggregates

The surface tension of living cells and tissues originates from the generation of nonequilibrium active stresses within the cell cytoskeleton. Here, using laser ablation, we generate gradients in the surface tension of cellular aggregates as models of simple tissues. These gradients of active surface stress drive large-scale and rapid toroidal motion. Subsequently, the motions spontaneously reverse as stresses reaccumulate and cells return to their original positions. Both forward and reverse motions resemble Marangoni flows in viscous fluids. However, the motions are faster than the timescales of viscoelastic relaxation, and the surface tension gradient is proportional to mechanical strain at the surface. Further, due to active stress, both the surface tension gradient and surface strain are dependent upon the volume of the aggregate. These results indicate that surface tension can induce rapid and highly correlated elastic deformations in the maintenance of tissue shape and configuration.

physics.bio-ph↗

arXiv2022

Hydroelastomers: soft, tough, highly swelling composites

Inspired by the cellular design of plant tissue, we present a new approach to make versatile, tough, highly water-swelling composites. We embed highly swelling hydrogel particles inside tough, water-permeable, elastomeric matrices. The resulting composites, which we call \emph{hydroelastomers}, show little softening as they swell, and have excellent fracture properties that match those of the best-performing, tough hydrogels. Our composites are straightforward to fabricate, based on commercial materials, and can easily be molded or extruded to form shapes with complex swelling geometries. Furthermore, there is a large design space available for making hydroelastomers, since one can use any hydrogel as the dispersed phase in the composite, including hydrogels with stimuli-responsiveness. These features should make hydroelastomers excellent candidates for use in soft robotics and swelling-based actuation, or as shape-morphing materials, while also being useful as hydrogel replacements in a wide range of other fields.

cond-mat.soft↗

arXiv2021

A robust method for quantification of surface elasticity in soft solids

We propose an approach to measure surface elastic constants of soft solids. Generally, this requires one to probe interfacial mechanics at around the elastocapillary length scale, which is typically microscopic. Deformations of microscopic droplets embedded in soft solids are particularly attractive, because they avoid intrinsic nonlinearities associated with previous experiments such as the equilibrium of contact lines and the relaxation of patterned surfaces. We derive analytical solutions for the shape of droplets under uniaxial deformation and for the radius of droplets upon hydrostatic inflation. We couple mechanical deformations to the dissolution of droplets to assess experimental sensitivities. Combined with experimental data from both modes of deformation, one should be able to reliably extract the complete set of isotropic surface material parameters following a specific minimization procedure.

cond-mat.soft↗

arXiv2021

Stress accumulation around ice in a temperature gradient

When materials freeze, they often undergo damage due to ice growth. Although this damage is commonly ascribed to the volumetric expansion of water upon freezing, it is usually driven by suction of water towards growing ice crystals. The freezing of this additional water can cause a large build up of stress. Here, we study this process by producing a stable ice/water interface in a controlled temperature gradient, and measuring the deformation of the confining boundary. Analysis of the deformation field reveals stresses applied to the boundary with $\mathcal{O}(μ\mathrm{m})$ resolution. Globally, stresses increase steadily over time as liquid water is transported to more deeply undercooled regions. Locally, stresses increase until ice growth is stalled by the confining stresses. In accordance with the Clapeyron equation, the local limiting stress is proportional to the local undercooling. These results are closely connected to the crystallization pressure for growing crystals and condensation pressure during liquid-liquid phase separation.

cond-mat.soft↗

arXiv2021

Dynamics of Spontaneous Wrapping of Microparticles by Floppy Lipid Membranes

Lipid membranes form the barrier between the inside and outside of cells and many of their subcompartments. As such, they bind to a wide variety of nano- and micrometer sized objects and, in the presence of strong adhesive forces, strongly deform and envelop particles. This wrapping plays a key role in many healthy and disease-related processes. So far, little work has focused on the dynamics of the wrapping process. Here, using a model system of micron-sized colloidal particles and giant unilamellar lipid vesicles with tunable adhesive forces, we measure the velocity of the particle during its wrapping process as well as the forces exerted on it by the lipid membrane. Dissipation at the contact line appears to be the main factor determining the wrapping velocity and time to wrap an object.

cond-mat.soft↗

arXiv2021

Measuring surface tensions of soft solids with huge contact-angle hysteresis

The equilibrium contact angle of a droplet resting on a solid substrate can reveal essential properties of the solid's surface. However, when the motion of a droplet on a surface shows significant hysteresis, it is generally accepted that the solid's equilibrium properties cannot be determined. Here, we describe a method to measure surface tensions of soft solids with strong wetting hysteresis. With independent knowledge of the surface tension of the wetting fluid and the linear-elastic response of the solid, the solid deformations under the contact line and the contact angle of a single droplet together reveal the difference in surface tension of the solid against the liquid and vapor phases. If the solid's elastic properties are unknown, then this surface tension difference can be determined from the change in substrate deformations with contact angle. These results reveal an alternate equilibrium contact angle, equivalent to the classic form of Young-Dupré, but with surface tensions in place of surface energies. We motivate and apply this approach with experiments on gelatin, a common hydrogel.

cond-mat.soft↗

arXiv2021

Structural Color from Solid-State Polymerization-Induced Phase Separation

Structural colors are produced by wavelength-dependent scattering of light from nanostructures. While living organisms often exploit phase separation to directly assemble structurally colored materials from macromolecules, synthetic structural colors are typically produced in a two-step process involving the sequential synthesis and assembly of building blocks. Phase separation is attractive for its simplicity, but applications are limited due to a lack of robust methods for its control. A central challenge is to arrest phase separation at the desired length scale. Here, we show that solid-state polymerization-induced phase separation can produce stable structures at optical length scales. In this process, a polymeric solid is swollen and softened with a second monomer. During its polymerization, the two polymers become immiscible and phase separate. As free monomer is depleted, the host matrix resolidifies and arrests coarsening. The resulting PS-PMMA composites have a blue or white appearance. We compare these biomimetic nanostructures to those in structurally-colored feather barbs, and demonstrate the flexibility of this approach by producing structural color in filaments and large sheets.

cond-mat.soft↗

arXiv2021

Surface tension and the strain-dependent topography of soft solids

When stretched in one direction, most solids shrink in the transverse directions. In soft silicone gels, however, we observe that small-scale topographical features grow upon stretching. A quantitative analysis of the topography shows that this counter-intuitive response is nearly linear, allowing us to tackle it through a small-strain analysis. We find that the surprising increase of small-scale topography with stretch is due to a delicate interplay of the bulk and surface responses to strain. Specifically, we find that surface tension changes as the material is deformed. This response is expected on general grounds for solid materials, but challenges the standard description of gel- and elastomer-surfaces.

cond-mat.soft↗

arXiv2021

Micromirror total internal reflection microscopy for high-performance single particle tracking at interfaces

Single particle tracking has found broad applications in the life and physical sciences, enabling the observation and characterisation of nano- and microscopic motion. Fluorescence-based approaches are ideally suited for high-background environments, such as tracking lipids or proteins in or on cells, due to superior background rejection. Scattering-based detection is preferable when localisation precision and imaging speed are paramount due to the in principle infinite photon budget. Here, we show that micromirror-based total internal reflection dark field microscopy enables background suppression previously only reported for interferometric scattering microscopy, resulting in nm localisation precision at 6 $μ$s exposure time for 20 nm gold nanoparticles with a 25 x 25 $μ$m$^{2}$ field of view. We demonstrate the capabilities of our implementation by characterizing sub-nm deterministic flows of 20 nm gold nanoparticles at liquid-liquid interfaces. Our results approach the optimal combination of background suppression, localisation precision and temporal resolution achievable with pure scattering-based imaging and tracking of nanoparticles at regular interfaces.

physics.optics↗

arXiv2021

Droplets sit and slide anisotropically on soft, stretched substrates

Anisotropically wetting substrates enable useful control of droplet behavior across a range of applications. Usually, these involve chemically or physically patterning the substrate surface, or applying gradients in properties like temperature or electrical field. Here, we show that a flat, stretched, uniform soft substrate also exhibits asymmetric wetting, both in terms of how droplets slide and in their static shape. Droplet dynamics are strongly affected by stretch: glycerol droplets on silicone substrates with a 23\% stretch slide 67\% faster in the direction parallel to the applied stretch than in the perpendicular direction. Contrary to classical wetting theory, static droplets in equilibrium appear elongated, oriented parallel to the stretch direction. Both effects arise from droplet-induced deformations of the substrate near the contact line.

cond-mat.soft↗

arXiv2020

Viscoelastic and poroelastic relaxations of soft solid surfaces

Understanding surface mechanics of soft solids, such as soft polymeric gels, is crucial in many engineering processes, such as dynamic wetting and adhesive failure. In these situations, a combination of capillary and elastic forces drives the motion, which is balanced by dissipative mechanisms to determine the rate. While shear rheology (i.e. viscoelasticity) has long been assumed to dominate the dissipation, recent works have suggested that compressibility effects (i.e. poroelasticity) could play roles in swollen networks. We use fast interferometric imaging to quantify the relaxation of surface deformations due to a displaced contact line. By systematically measuring the profiles at different time and length scales, we experimentally observe a crossover from viscoelastic to poroelastic surface relaxations.

cond-mat.soft↗

arXiv2020

Wrapping of Microparticles by Floppy Lipid Vesicles

Lipid membranes, the barrier defining living cells and many of their sub-compartments, bind to a wide variety of nano- and micro-meter sized objects. In the presence of strong adhesive forces, membranes can strongly deform and wrap the particles, an essential step in crossing the membrane for a variety of health and disease-related processes. A large body of theoretical and numerical work has focused on identifying the physical properties that underly wrapping. Using a model system of micron-sized colloidal particles and giant unilamellar lipid vesicles with tunable adhesive forces, we measure a wrapping phase diagram and make quantitative comparisons to theoretical models. Our data is consistent with a model of membrane-particle interactions accounting for the adhesive energy per unit area, membrane bending rigidity, particle size, and vesicle radius.

cond-mat.soft↗

arXiv2020

Surface tensiometry of phase separated protein and polymer droplets by the sessile drop method

Phase separated macromolecules play essential roles in many biological and synthetic systems. Physical characterization of these systems can be challenging because of limited sample volumes, particularly for phase-separated proteins. Here, we demonstrate that a classic method for measuring the surface tension of liquid droplets, based on the analysis of the shape of a sessile droplet, can be effectively scaled down for this application. The connection between droplet shape and surface tension relies on the density difference between the droplet and its surroundings. This can be determined with small sample volumes in the same setup by measuring the droplet sedimentation velocity. An interactive MATLAB script for extracting the capillary length from a droplet image is included in the ESI.

cond-mat.soft↗

arXiv2020

Switchable Adhesion of Soft Composites Induced by a Magnetic Field

Switchable adhesives have the potential to improve the manufacturing and recycling of parts and to enable new modes of motility for soft robots. Here, we demonstrate magnetically-switchable adhesion of a two-phase composite to non-magnetic objects. The composite's continuous phase is a silicone elastomer, and the dispersed phase is a magneto-rheological fluid. The composite is simple to prepare, and to mould to different shapes. When a magnetic field is applied, the magneto-rheological fluid develops a yield stress, which dramatically enhances the composite's adhesive properties. We demonstrate up to a nine-fold increase of the pull-off force of non-magnetic objects in the presence of a 250 mT field.

physics.app-ph↗

arXiv2020

Elastic stresses reverse Ostwald ripening

When liquid droplets nucleate and grow in a polymer network, compressive stresses can significantly increase their internal pressure, reaching values that far exceed the Laplace pressure. When droplets have grown in a polymer network with a stiffness gradient, droplets in relatively stiff regions of the network tend to dissolve, favoring growth of droplets in softer regions. Here, we show that this elastic ripening can be strong enough to reverse the direction of Ostwald ripening: large droplets can shrink to feed the growth of smaller ones. To numerically model these experiments, we generalize the theory of elastic ripening to account for gradients in solubility alongside gradients in mechanical stiffness.

cond-mat.soft↗

arXiv2020

Designing Refractive Index Fluids using the Kramers-Kronig Relations

For a number of optical applications, it is advantageous to precisely tune the refractive index of a liquid. Here, we harness a well-established concept in optics for this purpose. The Kramers-Kronig relation provides physical connection between the spectral variation of the (real) refractive index and the absorption coefficient. In particular a sharp spectral variation of the absorption coefficient gives rise to either an enhancement or reduction of the refractive index in the spectral vicinity of this variation. By using bright commodity dyes that fulfil this absorption requirement, we demonstrate the use of the Kramers-Kronig relation to predictively dial-in refractive index values in water solutions that are otherwise only attained by toxic specialised liquids.

physics.optics↗