The role of poroelastic diffusion in the transient wetting behavior of hydrogels.

Wetting and water absorption of hydrogels is often encountered in many applications. We seek to understand how wetting behavior can be affected by the time-dependent swelling of hydrogels. We measured the advancing contact angles of water droplets on hydrogels of varying thicknesses where thicker gels absorbed water more slowly. We also observed that, above a threshold advancing speed, water droplets would collapse into a lower contact angle state on the surface. We hypothesized that this collapse threshold speed is a result of competition between the poroelastic diffusion of water into the gel and the advance of the spreading droplet, the thickness of the surface, and the diffusion of water into the gel. Taking the ratio of the diffusion and advancing timescales results in a Peclet number with gel thickness as a characteristic length scale. Our results show that above a Peclet number of around 40, droplets will collapse on the surface across all gel thicknesses, confirming our hypothesis. This work provides simple insight to understand a complex time-dependent wetting phenomenon for a widely used hydrogel.

Correction: Quantifying the trade-off between stiffness and permeability in hydrogels.

Correction for 'Quantifying the trade-off between stiffness and permeability in hydrogels' by Yiwei Gao et al., Soft Matter, 2022, 18, 7735-7740, https://doi.org/10.1039/D2SM01215D.

Quantifying the trade-off between stiffness and permeability in hydrogels.

Hydrogels have a distinct combination of mechanical and water-transport behaviors. As hydrogels stiffen when they de-swell, they become less permeable. Here, we combine de Gennes' semi-dilute polymer theory with the Kozeny-Carman equation to develop a simple, succinct scaling law describing the relationship between mechanical stiffness and hydraulic permeability where permeability scales with stiffness to the -8/9 power. We find a remarkably close agreement between the scaling law and experimental results across four different polymer families with varied crosslinkings. This inverse relationship establishes a fundamental trade-off between permeability and stiffness.

How dynamic adsorption controls surfactant-enhanced boiling.

Improving boiling is challenging due to the unpredictable nature of bubbles. One way to enhance boiling is with surfactants, which alter the solid-liquid and liquid-vapor interfaces. The conventional wisdom established by previous studies suggests that heat transfer enhancement is optimized near the critical micelle concentration (CMC), which is an equilibrium property that depends on surfactant type. However, these studies only tested a limited number of surfactants over small concentration ranges. Here, we test a larger variety of nonionic and anionic surfactants over the widest concentration range and find that a universal, optimal concentration range exists, irrespective of CMC. To explain this, we show that surfactant-enhanced boiling is controlled by two competing phenomena: (1) the dynamic adsorption of surfactants to the interfaces and (2) the increase in liquid dynamic viscosity at very high surfactant concentrations. This dynamic adsorption is time-limited by the millisecond-lifetime of bubbles on the boiling surface-much shorter than the timescales required to see equilibrium behaviors such as CMC. At very high concentrations, increased viscosity inhibits rapid bubble growth, reducing heat transfer. We combine the effects of adsorption and viscosity through a simple proportionality, providing a succinct and useful understanding of this enhancement behavior for boiling applications.

Scaling laws to predict humidity-induced swelling and stiffness in hydrogels.

From pasta to biological tissues to contact lenses, gel and gel-like materials inherently soften as they swell with water. In dry, low-relative-humidity environments, these materials stiffen as they de-swell with water. Here, we use semi-dilute polymer theory to develop a simple power-law relationship between hydrogel elastic modulus and swelling. From this relationship, we predict hydrogel stiffness or swelling at arbitrary relative humidities. Our close predictions of properties of hydrogels across three different polymer mesh families at varying crosslinking densities and relative humidities demonstrate the validity and generality of our understanding. This predictive capability enables more rapid material discovery and selection for hydrogel applications in varying humidity environments.

Under pressure: Hydrogel swelling in a granular medium.

Hydrogels hold promise in agriculture as reservoirs of water in dry soil, potentially alleviating the burden of irrigation. However, confinement in soil can markedly reduce the ability of hydrogels to absorb water and swell, limiting their widespread adoption. Unfortunately, the underlying reason remains unknown. By directly visualizing the swelling of hydrogels confined in three-dimensional granular media, we demonstrate that the extent of hydrogel swelling is determined by the competition between the force exerted by the hydrogel due to osmotic swelling and the confining force transmitted by the surrounding grains. Furthermore, the medium can itself be restructured by hydrogel swelling, as set by the balance between the osmotic swelling force, the confining force, and intergrain friction. Together, our results provide quantitative principles to predict how hydrogels behave in confinement, potentially improving their use in agriculture as well as informing other applications such as oil recovery, construction, mechanobiology, and filtration.

Scaling Law for Cracking in Shrinkable Granular Packings.

Hydrated granular packings often crack into discrete clusters of grains when dried. Despite its ubiquity, an accurate prediction of cracking remains elusive. Here, we elucidate the previously overlooked role of individual grain shrinkage-a feature common to many materials-in determining crack patterning using both experiments and simulations. By extending classical Griffith crack theory, we obtain a scaling law that quantifies how cluster size depends on the interplay between grain shrinkage, stiffness, and size-applicable to a diverse array of shrinkable granular packings.

Crack formation and self-closing in shrinkable, granular packings.

Many clays, soils, biological tissues, foods, and coatings are shrinkable, granular materials: they are composed of packed, hydrated grains that shrink when dried. In many cases, these packings crack during drying, critically hindering applications. However, while cracking has been widely studied for bulk gels and packings of non-shrinkable grains, little is known about how packings of shrinkable grains crack. Here, we elucidate how grain shrinkage alters cracking during drying. Using experiments with model shrinkable hydrogel beads, we show that differential shrinkage can dramatically alter crack evolution during drying-in some cases, even causing cracks to spontaneously "self-close". In other cases, packings shrink without cracking or crack irreversibly. We developed both granular and continuum models to quantify the interplay between grain shrinkage, poromechanics, packing size, drying rate, capillarity, and substrate friction on cracking. Guided by the theory, we also found that cracking can be completely altered by varying the spatial profile of drying. Our work elucidates the rich physics underlying cracking in shrinkable, granular packings, and yields new strategies for controlling crack evolution.

Adsorption and Denaturation of Structured Polymeric Nanoparticles at an Interface.

Nanoparticles (NPs) have been widely applied in fields as diverse as energy conversion, photovoltaics, environment remediation, and human health. However, the adsorption and trapping of NPs interfaces is still poorly understood, and few studies have characterized the kinetics quantitatively. In many applications, such as drug delivery, understanding NP interactions at an interface is essential to determine and control adsorption onto targeted areas. Therapeutic NPs are especially interesting because their structures involve somewhat hydrophilic surface coronas, to prevent protein adsorption, and much more hydrophobic core phases. We initiated this study after observing aggregates of nanoparticles in dispersions where there had been exposure of the dispersion to air interfaces. Here, we investigate the evolution of NP attachment and structural evolution at the air-liquid interface over time scales from 100 ms to 10s of seconds. We document three distinct stages in NP adsorption. In addition to an early stage of free diffusion and a later one with steric adsorption barriers, we find a hitherto unrealized region where the interfacial energy changes due to surface "denaturation" or restructuring of the NPs at the interface. We adopt a quantitative model to calculate the diffusion coefficient, adsorption rate and barrier, and extent of NP hydrophobic core exposure at different stages. Our results deepen the fundamental understanding of the adsorption of structured NPs at an interface.

Predicting Surface Tensions of Surfactant Solutions from Statistical Mechanics.

The importance of surfactants to various industries necessitates a predictive understanding of their surface tension and adsorption behavior in terms of molecular characteristics. Previous models are highly empirical, require fitting parameters, and have limited applicability at various temperatures. Here, we provide a surface tension model based on statistical mechanics that (1) is thermodynamically consistent, (2) provides a higher predictive power, wherein surface tension can be calculated for any tail length, concentration, and temperature from molecular parameters, and (3) provides a physical understanding of the important molecular interactions at play. This model is applicable to both nonionic and ionic surfactants, where the effects of the electric double layer have been taken into account in the latter case. For nonionic surfactants, we were able to extend our model to predict dynamic surface tension as well. We have validated our model with tensiometry experiments for various surfactants, concentrations, and temperatures. In addition, we have validated our model with a diverse set of literature data, wherein agreement within a few mN M-1 and a correct prediction of phase change behavior is shown. The model could enable a more informed design of surfactant systems and serve as the theoretical basis for theory on more complex surfactant systems such as mixtures.

Porosimetry and packing morphology of vertically aligned carbon nanotube arrays via impedance spectroscopy.

Vertically aligned one-dimensional nanostructure arrays are promising in many applications such as electrochemical systems, solar cells, and electronics, taking advantage of high surface area per unit volume, nanometer length scale packing, and alignment leading to high conductivity. However, many devices need to optimize arrays for device performance by selecting an appropriate morphology. Developing a simple, non-invasive tool for understanding the role of pore volume distribution and interspacing would aid in the optimization of nanostructure morphologies in electrodes. In this work, we combined electrochemical impedance spectroscopy (EIS) with capacitance measurements and porous electrode theory to conduct in situ porosimetry of vertically aligned carbon nanotube (VA-CNT) forests non-destructively. We utilized the EIS measurements with a pore size distribution model to quantify the average and dispersion of inter-CNT spacing (Γ), stochastically, in carpets that were mechanically densified from [Formula: see text] tubes cm-2 to [Formula: see text] tubes cm-2. Our analysis predicts that the inter-CNT spacing ranges from over 100 ± 50 nm in sparse carpets to sub 10 ± 5 nm in packed carpets. Our results suggest that waviness of CNTs leads to variations in the inter-CNT spacing, which can be significant in sparse carpets. This methodology can be used to predict the performance of many nanostructured devices, including supercapacitors, batteries, solar cells, and semiconductor electronics.

Characterization of Adsorption Enthalpy of Novel Water-Stable Zeolites and Metal-Organic Frameworks.

Water adsorption is becoming increasingly important for many applications including thermal energy storage, desalination, and water harvesting. To develop such applications, it is essential to understand both adsorbent-adsorbate and adsorbate-adsorbate interactions, and also the energy required for adsorption/desorption processes of porous material-adsorbate systems, such as zeolites and metal-organic frameworks (MOFs). In this study, we present a technique to characterize the enthalpy of adsorption/desorption of zeolites and MOF-801 with water as an adsorbate by conducting desorption experiments with conventional differential scanning calorimetry (DSC) and thermogravimetric analyzer (TGA). With this method, the enthalpies of adsorption of previously uncharacterized adsorbents were estimated as a function of both uptake and temperature. Our characterizations indicate that the adsorption enthalpies of type I zeolites can increase to greater than twice the latent heat whereas adsorption enthalpies of MOF-801 are nearly constant for a wide range of vapor uptakes.

Turning bubbles on and off during boiling using charged surfactants.

Boiling--a process that has powered industries since the steam age--is governed by bubble formation. State-of-the-art boiling surfaces often increase bubble nucleation via roughness and/or wettability modification to increase performance. However, without active in situ control of bubbles, temperature or steam generation cannot be adjusted for a given heat input. Here we report the ability to turn bubbles 'on and off' independent of heat input during boiling both temporally and spatially via molecular manipulation of the boiling surface. As a result, we can rapidly and reversibly alter heat transfer performance up to an order of magnitude. Our experiments show that this active control is achieved by electrostatically adsorbing and desorbing charged surfactants to alter the wettability of the surface, thereby affecting nucleation. This approach can improve performance and flexibility in existing boiling technologies as well as enable emerging or unprecedented energy applications.