In fracture mechanics, polyacrylamide hydrogels have been widely used as a model material for experiments, benefited from its optical transparency, fracture brittleness, and low Rayleigh wave velocity. To describe the brittle fracture in the hydrogels, linear elastic fracture mechanics comes as the first choice. However, in soft materials such as hydrogels, the crack opening can be extremely large, leading to substantial geometric nonlinearity and material nonlinearity at the crack tip. Furthermore, poroelasticity may also modify the local mechanical state within the polymer network. Direct characterization of the kinematic fields and poroelastic effect at the crack tip is lacking. Here, based on a hybrid method of digital image correlation and particle tracking technique, we retrieved high-resolution 3D particle trajectories near the tip of a slowly propagating crack and measured the near-tip 3D kinematic fields, including the displacement fields, rotation fields, stretch fields, strain fields, and swelling fields. Results confirmed the complex multi-axial stretching near the crack tip and the substantial geometric nonlinearity, particularly on the two wakes of the crack where rotation exceeds $30^{\circ}$. Comparison between the measured and predicted displacement and strain fields, derived from linear elastic fracture mechanics, highlights a disagreement in the direct vicinity of the crack tip, particularly for displacement component $u_x$ and through-thickness strain component $\varepsilon_{zz}$. Significant swelling, due to the poroelastic solvent migration, is also observed, with a strong correlation to the local stretch. Our experimental method, without any assumption of the material properties, can be readily extended to study 3D crack tips in a huge varieties of materials, and our results can shed light on the fundamental fracture mechanics.
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. Furt…
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…
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 humiditie…
Hydrogel coatings absorb water vapor - or other solvents - and, as such, are good candidates for antifog applications. In the present study, the transfer of vapor from the atmosphere to hydrogel thin films is measured in a situation where water vapor flows alongside the coating which is set to a temperature lower that the ambient temperature. The effect of the physico-chemistry of the hydrogel film on the swelling kinetics is particularly investigated. By using model thin films of surface-grafted polymer networks with controlled thickness, varied crosslinks density, and varied affinity for wat…
Subjected to compressive stresses, soft polymers with stiffness gradients can display various buckling patterns. These compressive stresses can have different origins, like mechanical forces, temperature changes, or, for hydrogel materials, osmotic swelling. Here, we focus on the influence of the transient nature of osmotic swelling on the initiation of buckling in confined layered hydrogel structures. A constitutive model for transient hydrogel swelling is outlined and implemented as a user-subroutine for the commercial finite element software Abaqus. The finite element procedure is benchmark…
We derive a large-strain plate model that allows to describe transient, coupled processes involving elasticity and solvent migration, by performing a dimensional reduction of a three-dimensional poroelastic theory. We apply the model to polymer gel plates, for which a specific kinematic constraint and constitutive relations hold. Finally, we assess the accuracy of the plate model with respect to the parent three-dimensional model through two numerical benchmarks, solved by means of the finite element method. Our results show that the theory offers an efficient computational framework for the s…
In this work a continuum model for high frequency poroelastic longitudinal waves in hydrogels is presented. A viscoelastic force describing the interaction between the polymer network and the bounded water present in such materials is introduced. The model is tested by means of ultrasound wave speed and attenuation measurements in polyvinylalcohol hydrogel samples. The theory and experiments show that ultrasound attenuation decreases linearly with the increase of the water volume fraction "β" of the hydrogel. The introduction of the viscoelastic force between the bounded water and the polymer …
We report on the poroelastic indentation response of hydrogel thin films geometrically confined within contacts with rigid spherical probes of radii in the millimeter range. Poly(PEGMA) (poly(ethylene glycol)) methyl ether methacrylate), poly(DMA) (dimethylacrylamide) and poly(NIPAM) (\textit{N}-isopropylacrylamide) gel films with thickness less than 15 $μ$m were grafted onto glass substrates using a thiol-ene click chemistry route. Changes in the indentation depth under constant applied load were monitored over time as a function of the film thickness and the radius of curvature of the probe …
Biocompatible Microscale DNA Hydrogels with Programmable Swelling and Sequence-Specific Dissolution
Johns Hopkins University（约翰斯·霍普金斯大学）；Johns Hopkins University School of Medicine（约翰斯·霍普金斯大学医学院）；The Sidney Kimmel Comprehensive Cancer Center, Johns Hopkins Hospital（约翰斯·霍普金斯医院西德尼·基梅尔综合癌症中心）
Control of the swelling, chemical functionalization, and adhesivity of hydrogels are finding new applications in a wide range of material systems. We investigate experimentally the effect of adsorbed particles on hydrogels on the depinning of contact lines. In our experiments, a water drop containing polystyrene microspheres is deposited on a swelling hydrogel, which leads to the drop absorption and particle deposition. Two regimes are observed: a decreasing drop height with a pinned contact line followed by a receding contact line. We show that increasing the particles concentration increases…
Thermo-responsive hydrogels are a promising material for creating controllable actuators for use in micro-scale devices, since they expand and contract significantly (absorbing or expelling fluid) in response to relatively small temperature changes. Understanding such systems can be difficult because of the spatially- and temporally-varying properties of the gel, and the complex relationships between the fluid dynamics, elastic deformation of the gel and chemical interaction between the polymer and fluid. We address this using a poro-elastic model, considering the dynamics of a thermo-responsi…
Non-uniform swelling of polyelectrolyte hydrogels: effects of charge regulation
Wenzhou University（温州大学）；Zhejiang Key Laboratory of Soft Matter Biomedical Materials, Wenzhou Institute, University of Chinese Academy of Sciences（中国科学院大学温州研究院软物质生物医用材料浙江省重点实验室）；School of Physical Sciences, University of Chinese Academy of Sciences（中国科学院大学物理科学学院）；School of Physics and Astronomy, & Center for Physics and Chemistry of Living Systems, Tel Aviv University（特拉维夫大学物理与天文学学院及生命系统物理化学中心）；School of Sino-German Engineering, Shanghai Technical Institute of Electronics and Information（上海电子与信息工程技术学院中德工程学院）
Covalent functionalisation of collagen has been shown to be a promising strategy to adjust the mechanical properties of highly swollen collagen hydrogels. At the same time, secondary interactions between for example, amino acidic terminations or introduced functional groups also play an important role and are often challenging to predict and control. To explore this challenge, 4-vinylbenzyl chloride (4VBC) and methacrylic anhydride (MA) were reacted with type I collagen, and the swelling and rheological properties of resulting photo activated hydrogel systems investigated. 4VBC-based hydrogels…
We report on the frictional behaviour of thin poly(dimethylacrylamide) (PDMA) hydrogels films grafted on glass substrates in sliding contact with a glass spherical probe. Friction experiments are carried out at various velocities and applied normal loads with the contact fully immersed in water. In addition to friction force measurements, a novel optical set-up is designed to image the shape of the contact under steady-state sliding. The velocity-dependence of both friction force $F_t$ and contact shape is found to be controlled by a Péclet number Pe defined as the ratio of the time $τ$ needed…
A polymer network can imbibe water, forming an aggregate called hydrogel, and undergo large and inhomogeneous deformation with external mechanical constraint. Due to the large deformation, nonlinearity plays a crucial role, which also causes the mathematical difficulty for obtaining analytical solutions. Based on an existing model for equilibrium states of a swollen hydrogel with a core-shell structure, this paper seeks analytical solutions of the deformations by perturbation methods for three cases, i.e. free-swelling, nearly free-swelling and general inhomogeneous swelling. Particularly for …
We investigate the swelling dynamics driven by solvent absorption in a hydrogel sphere immersed in a solvent bath, through an accurate computational model and numerical study. We extensively describe the transient process from dry to wet and discuss the onset of surface instabilities through a measure of the lack of smoothness of the outer surface and a morphological pattern of that surface with respect to the two material parameters driving the swelling dynamics.
Hydrogels have had a profound impact in the fields of tissue engineering, drug delivery, and materials science as a whole. Due to the network architecture of these materials, imbibement with water often results in uniform swelling and isotropic expansion which scales with the degree of cross-linking. However, the development of internal stresses during swelling can have dramatic consequences, leading to surface instabilities as well as rupture or bursting events. To better understand hydrogel behavior, macroscopic mechanical characterization techniques (e.g.\ tensile testing, rheometry) are of…
Tough adhesive hydrogels find broad applications in engineering and medicine. Such hydrogels feature high resistance against both cohesion and adhesion failure. The superior fracture properties may, however, deteriorate when the hydrogels swell upon exposure of water. The underlying correlation between the polymer fraction and fracture properties of tough adhesive hydrogels remains largely unexplored. Here we study how the cohesion and adhesion energies of a tough adhesive hydrogel evolve with the swelling process. The results reveal a similar scaling law of the two quantities on the polymer f…
Tissue engineering aims to grow artificial tissues \emph{in vitro} to replace those in the body that have been damaged through age, trauma or disease. A recent approach to engineer artificial cartilage involves seeding cells within a scaffold consisting of an interconnected 3D-printed lattice of polymer fibres combined with a cast or printed hydrogel, and subjecting the construct (cell-seeded scaffold) to an applied load in a bioreactor. A key question is to understand how the applied load is distributed throughout the construct. To address this, we employ homogenisation theory to derive equat…
Linear poroelastic response of thin permeable gel films
Ecole des Ponts Paris Tech（巴黎路桥学校）；Université Gustave Eiffel（居斯塔夫埃菲尔大学）；CNRS（法国国家科学研究中心）；ESPCI Paris（巴黎物理化工国立高等学院）；Université PSL（巴黎文理研究大学）；Institut Pierre-Gilles de Gennes（皮埃尔-吉勒·德热纳研究所）；Univ. Bordeaux（波尔多大学）；LOMA（光学与分子力学实验室）
When a rigid object approaches a soft material in a viscous fluid, hydrodynamic stresses arise in the lubricated contact region and deform the soft material. The elastic deformation modifies in turn the flow, hence generating a soft-lubrication coupling. Moreover, soft elastomers and gels are often porous. These materials may be filled with solvent or uncrosslinked polymer chains, and might be permeable to the surrounding fluid, which complexifies further the description. Here, we derive the point-force response of a semi-infinite and permeable poroelastic substrate. Then, we use this fundamen…
Brittle materials fail catastrophically. In consequence of their limited flaw-tolerance, failure occurs by localized fracture and is typically a dynamic process. Recently, experiments on epithelial cell monolayers have revealed that this scenario can be significantly modified when the material susceptible to cracking is adhered to a hydrogel substrate. Thanks to the hydraulic coupling between the brittle layer and the poroelastic substrate, such a composite can develop a toughening mechanism that relies on the simultaneous growth of multiple cracks. Here, we study this remarkable behaviour by …
In order to establish defined biomimetic systems, type I collagen was functionalised with 1,3-Phenylenediacetic acid (Ph) as aromatic, bifunctional segment. Following investigation on molecular organization and macroscopic properties, material functionalities, i.e. degradability and bioactivity, were addressed, aiming at elucidating the potential of this collagen system as mineralization template. Functionalised collagen hydrogels demonstrated a preserved triple helix conformation. Decreased swelling ratio and increased thermo-mechanical properties were observed in comparison to state-of-the-a…
Hydrogels have the ability to undergo large deformations and yet fail like brittle materials. The development of biocompatible hydrogels with high strength and toughness is an ongoing challenge in many applications. We crosslinked bovine gelatin using glutaraldehyde (control) and methylglyoxal (MGO) and assessed changes in their fracture toughness. Swelling experiments show ~710% retention of water in MGO hydrogels as compared to ~450% in control specimens. We used FTIR to identify the presence of chemical groups that may be involved in the crosslinking of gelatin gels. Scanning electron micro…
