Network physics of attractive colloidal gels: Resilience, rigidity, and phase diagram.

Colloidal gels exhibit solid-like behavior at vanishingly small fractions of solids, owing to ramified space-spanning networks that form due to particle-particle interactions. These networks give the gel its rigidity, and with stronger attractions the elasticity grows as well. The emergence of rigidity can be described through a mean field approach; nonetheless, fundamental understanding of how rigidity varies in gels of different attractions is lacking. Moreover, recovering an accurate gelation phase diagram based on the system's variables has been an extremely challenging task. Understanding the nature of colloidal clusters, and how rigidity emerges from their connections is key to controlling and designing gels with desirable properties. Here, we employ network analysis tools to interrogate and characterize the colloidal structures. We construct a particle-level network, having all the spatial coordinates of colloids with different attraction levels, and also identify polydisperse rigid fractal clusters using a Gaussian mixture model, to form a coarse-grained cluster network that distinctly shows main physical features of the colloidal gels. A simple mass-spring model then is used to recover quantitatively the elasticity of colloidal gels from these cluster networks. Interrogating the resilience of these gel networks shows that the elasticity of a gel (a dynamic property) is directly correlated to its cluster network's resilience (a static measure). Finally, we use the resilience investigations to devise [and experimentally validate] a fully resolved phase diagram for colloidal gelation, with a clear solid-liquid phase boundary using a single volume fraction of particles well beyond this phase boundary.

Brittle and ductile yielding in soft materials.

Many soft materials yield under mechanical loading, but how this transition from solid-like behavior to liquid-like behavior occurs can vary significantly. Understanding the physics of yielding is of great interest for the behavior of biological, environmental, and industrial materials, including those used as inks in additive manufacturing and muds and soils. For some materials, the yielding transition is gradual, while others yield abruptly. We refer to these behaviors as being ductile and brittle. The key rheological signatures of brittle yielding include a stress overshoot in steady-shear-startup tests and a steep increase in the loss modulus during oscillatory amplitude sweeps. In this work, we show how this spectrum of yielding behaviors may be accounted for in a continuum model for yield stress materials by introducing a parameter we call the brittility factor. Physically, an increased brittility decreases the contribution of recoverable deformation to plastic deformation, which impacts the rate at which yielding occurs. The model predictions are successfully compared to results of different rheological protocols from a number of real yield stress fluids with different microstructures, indicating the general applicability of the phenomenon of brittility. Our study shows that the brittility of soft materials plays a critical role in determining the rate of the yielding transition and provides a simple tool for understanding its effects under various loading conditions.

Controlling swelling in mixed transport polymers through alkyl side-chain physical cross-linking.

Semiconducting conjugated polymers bearing glycol side chains can simultaneously transport both electronic and ionic charges with high charge mobilities, making them ideal electrode materials for a range of bioelectronic devices. However, heavily glycolated conjugated polymer films have been observed to swell irreversibly when subjected to an electrochemical bias in an aqueous electrolyte. The excessive swelling can lead to the degradation of their microstructure, and subsequently reduced device performance. An effective strategy to control polymer film swelling is to copolymerize glycolated repeat units with a fraction of monomers bearing alkyl side chains, although the microscopic mechanism that constrains swelling is unknown. Here we investigate, experimentally and computationally, a series of archetypal mixed transporting copolymers with varying ratios of glycolated and alkylated repeat units. Experimentally we observe that exchanging 10% of the glycol side chains for alkyl leads to significantly reduced film swelling and an increase in electrochemical stability. Through molecular dynamics simulation of the amorphous phase of the materials, we observe the formation of polymer networks mediated by alkyl side-chain interactions. When in the presence of water, the network becomes increasingly connected, counteracting the volumetric expansion of the polymer film.

Rigorous Progress in Coarse-Graining.

Low-resolution coarse-grained (CG) models provide remarkable computational and conceptual advantages for simulating soft materials. In principle, bottom-up CG models can reproduce all structural and thermodynamic properties of atomically detailed models that can be observed at the resolution of the CG model. This review discusses recent progress in developing theory and computational methods for achieving this promise. We first briefly review variational approaches for parameterizing interaction potentials and their relationship to machine learning methods. We then discuss recent approaches for simultaneously improving both the transferability and thermodynamic properties of bottom-up models by rigorously addressing the density and temperature dependence of these potentials. We also briefly discuss exciting progress in modeling high-resolution observables with low-resolution CG models. More generally, we highlight the essential role of the bottom-up framework not only for fundamentally understanding the limitations of prior CG models but also for developing robust computational methods that resolve these limitations in practice.

Microscopic dynamics underlying the stress relaxation of arrested soft materials.

Arrested soft materials such as gels and glasses exhibit a slow stress relaxation with a broad distribution of relaxation times in response to linear mechanical perturbations. Although this macroscopic stress relaxation is an essential feature in the application of arrested systems as structural materials, consumer products, foods, and biological materials, the microscopic origins of this relaxation remain poorly understood. Here, we elucidate the microscopic dynamics underlying the stress relaxation of such arrested soft materials under both quiescent and mechanically perturbed conditions through X-ray photon correlation spectroscopy. By studying the dynamics of a model associative gel system that undergoes dynamical arrest in the absence of aging effects, we show that the mean stress relaxation time measured from linear rheometry is directly correlated to the quiescent superdiffusive dynamics of the microscopic clusters, which are governed by a buildup of internal stresses during arrest. We also show that perturbing the system via small mechanical deformations can result in large intermittent fluctuations in the form of avalanches, which give rise to a broad non-Gaussian spectrum of relaxation modes at short times that is observed in stress relaxation measurements. These findings suggest that the linear viscoelastic stress relaxation in arrested soft materials may be governed by nonlinear phenomena involving an interplay of internal stress relaxations and perturbation-induced intermittent avalanches.

Advances in Biocarbon and Soft Material Assembly for Enthalpy Storage: Fundamentals, Mechanisms, and Multimodal Applications.

High-value-added biomass materials like biocarbon are being actively pursued integrating them with soft materials in a broad range of advanced renewable energy technologies owing to their advantages, such as lightweight, relatively low-cost, diverse structural engineering applications, and high energy storage potential. Consequently, the hybrid integration of soft and biomass-derived materials shall store energy to mitigate intermittency issues, primarily through enthalpy storage during phase change. This paper introduces the recent advances in the development of natural biomaterial-derived carbon materials in soft material assembly and its applications in multidirectional renewable energy storage. Various emerging biocarbon materials (biochar, carbon fiber, graphene, nanoporous carbon nanosheets (2D), and carbon aerogel) with intrinsic structures and engineered designs for enhanced enthalpy storage and multimodal applications are discussed. The fundamental design approaches, working mechanisms, and feature applications, such as including thermal management and electromagnetic interference shielding, sensors, flexible electronics and transparent nanopaper, and environmental applications of biocarbon-based soft material composites are highlighted. Furthermore, the challenges and potential opportunities of biocarbon-based composites are identified, and prospects in biomaterial-based soft materials composites are presented.

Uniform, Strain-Free, Large-Scale Graphene and h-BN Monolayers Enabled by Hydrogel Substrates.

Translation of the unique properties of 2D monolayers from non-scalable micron-sized samples to macroscopic scale is a longstanding challenge obstructed by the substrate-induced strains, interface nonuniformities, and sample-to-sample variations inherent to the scalable fabrication methods. So far, the most successful strategies to reduce strain in graphene are the reduction of the interface roughness and lattice mismatch by using hexagonal boron nitride (h-BN), with the drawback of limited uniformity and applicability to other 2D monolayers, and liquid water, which is not compatible with electronic devices. This work demonstrates a new class of substrates based on hydrogels that overcome these limitations and excel h-BN and water substrates at strain relaxation enabling superiorly uniform and reproducible centimeter-sized sheets of unstrained monolayers. The ultimate strain relaxation and uniformity are rationalized by the extreme structural adaptability of the hydrogel surface owing to its high liquid content and low Young's modulus, and are universal to all 2D materials irrespective of their crystalline structure. Such platforms can be integrated into field effect transistors and demonstrate enhanced charge carrier mobilities in graphene. These results present a universal strategy for attaining uniform and strain-free sheets of 2D materials and underline the opportunities enabled by interfacing them with soft matter.

Soft multi-layer actuators integrated with the functions of electrical energy harvest and storage.

Soft multi-layer actuators are smart, lightweight, and flexible, which can be used in a wide range of fields such as artificial muscles, advanced medical devices, and wearable devices. The research on the actuation property of the soft actuators has made significant progress, paving the way for the controllable motions of the actuators. However, compared with the intelligence and adaptability of life in nature, these actuators still have the problem of insufficient intelligence. The phenomenon is reflected in a lack of continuous supply of energy. Therefore, it has become a development trend to combine functions such as energy harvesting, storage, and conversion with actuators to build intelligent actuators. This concept presents a synopsis of the advancements made in soft actuators that have been coupled with the capabilities of electrical energy harvesting and storage. The design concepts and typical applications of this soft smart actuators are introduced in detail. Finally, the future research directions and applications of smart actuators are prospected from our perspective.

Soft Actuators and Actuation: Design, Synthesis, and Applications.

Soft actuators are one of the most promising technological advancements with potential solutions to diverse fields' day-to-day challenges. Soft actuators derived from hydrogel materials possess unique features such as flexibility, responsiveness to stimuli, and intricate deformations, making them ideal for soft robotics, artificial muscles, and biomedical applications. This review provides an overview of material composition and design techniques for hydrogel actuators, exploring 3D printing, photopolymerization, cross-linking, and microfabrication methods for improved actuation. It examines applications of hydrogel actuators in biomedical, soft robotics, bioinspired systems, microfluidics, lab-on-a-chip devices, and environmental, and energy systems. Finally, it discusses challenges, opportunities, advancements, and regulatory aspects related to hydrogel actuators.

Performance of molecular crystals in conversion of light to mechanical work.

Dynamic molecular crystals have recently received ample attention as an emerging class of energy-transducing materials, yet have fallen short of developing into fully realized actuators. Through the trans-cis surface isomerization of three crystalline azobenzene materials, here, we set out to extensively characterize the light-to-work energy conversion of photoinduced bending in molecular crystals. We distinguish the azobenzene single crystals from commonly used actuators through quantitative performance evaluation and specific performance indices. Bending molecular crystals have an operating range comparable to that of microactuators such as microelectromechanical systems and a work-generating capacity and dynamic performance that qualifies them to substitute micromotor drivers in mechanical positioning and microgripping tasks. Finite element modeling, applied to determine the surface photoisomerization parameters, allowed for predicting and optimizing the mechanical response of these materials. Utilizing mechanical characterization and numerical simulation tools proves essential in accelerating the introduction of dynamic molecular crystals into soft microrobotics applications.

Elastic amplification of the Rayleigh-Taylor instability in solidifying melts.

The concomitant mechanical deformation and solidification of melts are relevant to a broad range of phenomena. Examples include the preparation of cotton candy, the atomization of metals, the manufacture of glass fibers, and the formation of elongated structures in volcanic eruptions known as Pele's hair. Usually, solid-like deformations during solidification are neglected as the melt is much more malleable in its initial liquid-like form. Here we demonstrate how elastic deformations in the midst of solidification, i.e., while the melt responds as a very soft solid ([Formula: see text] Pa), can lead to the formation of previously unknown periodic structures. Namely, we generate an array of droplets on a thin layer of liquid elastomer melt coated on the outside of a rotating cylinder through the Rayleigh-Taylor instability. Then, as the melt cures and goes through its gelation point, the rotation speed is increased and the drops stretch into hairs. The ongoing solidification eventually hardens the material, permanently "freezing" these elastic deformations into a patterned solid. Using experiments, simulation, and theory, we demonstrate that the formation of our two-step patterns can be rationalized when combining the tools from fluid mechanics, elasticity, and statistics. Our study therefore provides a framework to analyze multistep pattern formation processes and harness them to assemble complex materials.

Programmable droplet manipulation and wetting with soft magnetic carpets.

The ability to regulate interfacial and wetting properties is highly demanded in anti-icing, anti-biofouling, and medical and energy applications. Recent work on liquid-infused systems achieved switching wetting properties, which allow us to turn between slip and pin states. However, patterning the wetting of surfaces in a dynamic fashion still remains a challenge. In this work, we use programmable wetting to activate and propel droplets over large distances. We achieve this with liquid-infused soft magnetic carpets (SMCs) that consist of pillars that are responsive to external magnetic stimuli. Liquid-infused SMCs, which are sticky for a water droplet, become slippery upon application of a magnetic field. Application of a patterned magnetic field results in a patterned wetting on the SMC. A traveling magnetic field wave translates the patterned wetting on the substrate, which allows droplet manipulation. The droplet speed increases with an increased contact angle and with the droplet size, which offers a potential method to sort and separate droplets with respect to their contact angle or size. Furthermore, programmable control of the droplet allows us to conduct reactions by combining droplets loaded with reagents. Such an ability of conducting small-scale reactions on SMCs has the potential to be used for automated analytical testing, diagnostics, and screening, with a potential to reduce the chemical waste.

Complex Pathways Drive Pluripotent Fmoc-Leucine Self-Assemblies.

Nature uses complex self-assembly pathways to access distinct functional non-equilibrium self-assemblies. This remarkable ability to steer same set of biomolecules into different self-assembly states is done by avoiding thermodynamic pit. In synthetic systems, on demand control over 'Pathway Complexity' to access self-assemblies different from equilibrium structures remains challenging. Here we show versatile non-equilibrium assemblies of the same monomer via alternate assembly pathways. The assemblies nucleate using non-classical or classical nucleation routes into distinct metastable (transient hydrogels), kinetic (stable hydrogels) and thermodynamic structures [(poly)-crystals and 2D sheets]. Initial chemical and thermal inputs force the monomers to follow different assembly pathways and form soft-materials with distinct molecular arrangements than at equilibrium. In many cases, equilibrium structures act as thermodynamic sink which consume monomers from metastable structures giving transiently formed materials. This dynamics can be tuned chemically or thermally to slow down the dissolution of transient hydrogel, or skip the intermediate hydrogel altogether to reach final equilibrium assemblies. If required this metastable state can be kinetically trapped to give strong hydrogel stable over days. This method to control different self-assembly states can find potential use in similar biomimetic systems to access new materials for various applications.

Molecular Syringe for Cargo Photorelease: Red-Light-Triggered Supramolecular Hydrogel.

Photochromic supramolecular hydrogels are versatile materials that show macroscopic effects upon irradiation, like liquefaction or shape changes. Here, we demonstrate a simple photochromic cyclic dipeptide (2,5-diketopiperazine-based) supergelator, composed of (S)-lysine and an azobenzene analogue of phenylalanine, that forms supramolecular hydrogels even at 0.1 wt% loading. The gels can physically encapsulate cargo molecules and release them to the environment in a controllable manner upon irradiation with red light, thus working as a "molecular syringe". As the material is biocompatible and operational in the "therapeutic window" of light (>650 nm) that deeply penetrates soft human tissues, it is applicable to smart drug-delivery systems.

Soft, skin-interfaced microfluidic systems with integrated immunoassays, fluorometric sensors, and impedance measurement capabilities.

Soft microfluidic systems that capture, store, and perform biomarker analysis of microliter volumes of sweat, in situ, as it emerges from the surface of the skin, represent an emerging class of wearable technology with powerful capabilities that complement those of traditional biophysical sensing devices. Recent work establishes applications in the real-time characterization of sweat dynamics and sweat chemistry in the context of sports performance and healthcare diagnostics. This paper presents a collection of advances in biochemical sensors and microfluidic designs that support multimodal operation in the monitoring of physiological signatures directly correlated to physical and mental stresses. These wireless, battery-free, skin-interfaced devices combine lateral flow immunoassays for cortisol, fluorometric assays for glucose and ascorbic acid (vitamin C), and digital tracking of skin galvanic responses. Systematic benchtop evaluations and field studies on human subjects highlight the key features of this platform for the continuous, noninvasive monitoring of biochemical and biophysical correlates of the stress state.

Liquid Crystal Emulsions: A Versatile Platform for Photonics, Sensing, and Active Matter.

The self-assembly of liquid crystals (LCs) is a fascinating method for controlling the organization of discrete molecules into nanostructured functional materials. Although LCs are traditionally processed in thin films, their confinement within micrometre-sized droplets has recently revealed new properties and functions, paving the way for next-generation soft responsive materials. These recent findings have unlocked a wealth of unprecedented applications in photonics (e.g. reflectors, lasing materials), sensing (e.g. biomolecule and pathogen detection), soft robotics (e.g. micropumps, artificial muscles), and beyond. This Minireview focuses on recent developments in LC emulsion designs and highlights a variety of novel potential applications. Perspectives on the opportunities and new directions for implementing LC emulsions in future innovative technologies are also provided.

Bioinspired Freeze-Tolerant Soft Materials: Design, Properties, and Applications.

In nature, many biological organisms have developed the exceptional antifreezing ability to survive in extremely cold environments. Inspired by the freeze resistance of these organisms, researchers have devoted extensive efforts to develop advanced freeze-tolerant soft materials and explore their potential applications in diverse areas such as electronic skin, soft robotics, flexible energy, and biological science. Herein, a comprehensive overview on the recent advancement of freeze-tolerant soft materials and their emerging applications from the perspective of bioinspiration and advanced material engineering is provided. First, the mechanisms underlying the freeze tolerance of cold-enduring biological organisms are introduced. Then, engineering strategies for developing antifreezing soft materials are summarized. Thereafter, recent advances in freeze-tolerant soft materials for different technological applications such as smart sensors and actuators, energy harvesting and storage, and cryogenic medical applications are presented. Finally, future challenges and opportunities for the rapid development of bioinspired freeze-tolerant soft materials are discussed.

Non-Globular Organic Ionic Plastic Crystal Containing a Crown-Ether Moiety - Tuning Its Behaviour Using Sodium Salts.

Organic ionic plastic crystals (OIPCs) are a class of soft materials showing positional order while still allowing orientational freedom. Due to their motional freedom in the solid state, they possess plasticity, non-flammability and high ionic conductivity. OIPC behavior is typically exhibited by 'simple' globular molecules allowing molecular rotation, whereas the interactions that govern the formation of OIPC phases in complex non-globular molecules are less understood. To better understand these interactions, a new family of non-globular OIPCs containing a 15-crown-5 ether moiety was synthetized and characterized. The 15C5BA molecule prepared does not exhibit the sought-after behavior because of its non-globular nature and strong intermolecular H-bonds that restrict orientational motion. However, the OIPC behavior was successfully obtained through complexation of the crown-ether moiety with sodium salts containing chaotropic anions. Those anions weaken the interactions between the molecules, allowing rotational freedom and tuning of the thermal and morphological properties of the OIPC.

Polyoxometalate-Containing Supramolecular Gels.

Supramolecular gels are important soft materials with various applications, which are fabricated through hydrogen bonding, π-π stacking, electrostatic interactions, or host-guest interactions. Introducing functional groups, especially inorganic components, is an efficient strategy to obtain gels with robust architecture and high performance. Polyoxometalates (POMs), as a class of negatively-charged clusters, have defined structures and multiple interaction sites, resulting in their potential as building blocks for constructing POM-containing supramolecular gels. The introduction of POMs into gels not only provides strong driving forces for the formation of gels due to the characteristics of charged cluster and oxygen-rich surface, but also brings new properties sourcing from the unique electronic structures of POMs. Though many POM-containing gels have been reported, a comprehensive review is still absent. Herein, the concept of POM-containing gels is discussed, following with the design strategies and driving forces. To better understand the results in the literature, detailed examples, which are classified into several categories based on the types of organic components, are presented to illustrate the gelation process and gel structures. Moreover, applications of POM-containing gels in energy chemistry, sustainable chemistry, and other aspects are also reviewed, as well as the future developments of this field.

Sideways and stable crack propagation in a silicone elastomer.

We have discovered a peculiar form of fracture that occurs in a highly stretchable silicone elastomer (Smooth-On Ecoflex 00-30). Under certain conditions, cracks propagate in a direction perpendicular to the initial precut and in the direction of the applied load. In other words, the crack deviates from the standard trajectory and instead propagates perpendicular to that trajectory. The crack arrests stably, and thus the material ahead of the crack front continues to sustain load, thereby enabling enormous stretchabilities. We call this phenomenon "sideways" and stable cracking. To explain this behavior, we first perform finite-element simulations that demonstrate a propensity for sideways cracking, even in an isotropic material. The simulations also highlight the importance of crack-tip blunting on the formation of sideways cracks. Next, we provide a hypothesis on the origin of sideways cracking that relates to microstructural anisotropy (in a nominally isotropic elastomer). To substantiate this hypothesis, we transversely prestretch samples to various extents before fracture testing, as to determine the influence of microstructural arrangement (chain alignment and strain-induced crystallization) on fracture energy. We also perform microstructural characterization that indicates that significant chain alignment and strain-induced crystallization indeed occur in this material upon stretching. We conclude by characterizing how a number of loading conditions, such as sample geometry and strain rate, affect this phenomenon. Overall, this paper provides fundamental mechanical insight into basic phenomena associated with fracture of elastomers.