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The heterogeneous structure that exists in virtually all hydrogels has a significant influence on the resulting strength and toughness. While the internal structure has been observed with electron microscopy, it is difficult to measure the in situ local polymer concentration in the native swollen state. In this study, a modified microelectrode technique (MET) was employed to measure the Donnan potential of a heterogeneous hydrogel with a phase-separated structure. With this method, we succeeded in observing quantitative in situ polymer concentrations ranging from 10.2 mu mol/L to several hundred mmol/L. From the obtained concentration profiles, we could successfully evaluate the internal phase-separated structure with a resolution of less than 0.8 mu m. Using MET, we could estimate the average activity coefficient of the hydrogel, and we found a difference in concentration between the dense and sparse phases. We demonstrate that MET is a powerful method that can locally and quantitatively measure the polyelectrolyte concentration distribution within hydrogels. Furthermore, this method can be applied to cells and organs in vivo due to their similarities with polyelectrolytes. Enabling the in situ determination of the internal structures of biomaterials could have important implications toward the characterization of damaged and diseased tissues on the local scale.

The high fracture energy of tough soft materials can be attributed to the large energy dissipation zone around the crack tip. Hence, quantitative characterization of energy dissipation is the key to soft matter fracture mechanics. In this study, we quantified the energy dissipation in the damage zone of a double-network (DN) hydrogel using a mechanochemical technique based on mechanoradical polymerization combined with confocal fluorescence microscopy. We found that, in addition to energy dissipation in a relatively narrow yield region, the dissipation in the wide preyielding region and the intrinsic fracture energy also has a large contribution to the fracture energy. Moreover, the fracture energy of a prestretched sample, in which the dissipative capacity is nearly depleted, suggests that the intrinsic fracture energy is higher than the fracture energy of the second network. These findings modify the previous understanding that the fracture energy of DN gels is dominated by the energy of the yielding zone formation.

Summary The toughness of composite materials is size dependent below a critical load transfer length (lT). Fiber-reinforced viscoelastic polymers are uniquely suited to study the size-limited regime because the lT of these soft composites can be as high as several centimeters, in contrast to traditional composites where lT is extremely small, allowing a large window for macroscale characterization. In this work, we elucidate the parameters that influence the toughness of soft composites when failure is governed by a fiber pullout-induced matrix-fracture mechanism. We ultimately demonstrate three important points: (1) fiber-reinforced viscoelastic polymers can possess high toughness, even at dimensions well below lT, (2) significant toughness amplification occurs due to the presence of fibers, even when the fracture process consists solely of matrix rupture, and (3) the composite toughness in the fiber pullout region can be predicted from easily attainable component parameters.

Longer and stronger; stiff but not brittle Hydrogels are highly water-swollen, cross-linked polymers. Although they can be highly deformed, they tend to be weak, and methods to strengthen or toughen them tend to reduce stretchability. Two papers now report strategies to create tough but deformable hydrogels (see the Perspective by Bosnjak and Silberstein). Wang et al . introduced a toughening mechanism by storing releasable extra chain length in the stiff part of a double-network hydrogel. A high applied force triggered the opening of cycling strands that were only activated at high chain extension. Kim et al . synthesized acrylamide gels in which dense entanglements could be achieved by using unusually low amounts of water, cross-linker, and initiator during the synthesis. This approach improves the mechanical strength in solid form while also improving the wear resistance once swollen as a hydrogel. —MSL

We propose a new concept that utilizes the difference in Poisson's ratio between component materials as a strengthening mechanism that increases the effectiveness of the sacrificial bond toughening mechanism in macroscale double-network (Macro-DN) materials. These Macro-DN composites consist of a macroscopic skeleton imbedded within a soft elastic matrix. We varied the Poisson's ratio of the reinforcing skeleton by introducing auxetic or honeycomb functional structures that results in Poisson’s ratio mismatch between the skeleton and matrix. During uniaxial tensile experiments, high strength and toughness were achieved due to two events: (1) multiple internal bond fractures of the skeleton (like sacrificial bonds in classic DN gels) and (2) significant, biaxial deformation of the matrix imposed by the functional skeleton. The Macro-DN composite with auxetic skeleton exhibits up to 4.2 times higher stiffness and 4.4 times higher yield force than the sum of the component materials. The significant improvement in mechanical performance is correlated to the large mismatch in Poisson's ratio between component materials, and the enhancement is especially noticeable in the low-stretch regime. The strengthening mechanism reported here based on Poisson's ratio mismatch can be widely used for soft materials regardless of chemical composition and will improve the mechanical properties of elastomer and hydrogel systems.

Biological tissues usually have complex superstructures and elaborated functionalities. However, creating superstructures in soft and wet hydrogels is challenging because of the absence of effective approaches to control the molecular orientation. Here we introduce a method to create superstructures in photonic hydrogels comprising lamellar bilayers intercalated in the cross-linked polymer network. The orientation of lamellar bilayers in the photonic gel, which are sensitive to shear, is modulated by applying a gradient shear field on the precursor solution using a customized rheometer. The difference in orientation of lamellar bilayers leads to swelling mismatch in the radial direction, endowing the disk-shape hydrogel with a macroscopic flower-like shape with a central dome and an edge petal, along with a bright photonic color. By characterization of the swelling anisotropy of the radial profile, the shear rate required for the unidirectional orientation of lamellar bilayers was extracted. Moreover, a delayed polymerization experiment was designed to measure the lifetime of aligned lamellar bilayers, which reveals the domain size of lamellar bilayers in the precursor solution. Furthermore, we also demonstrated that the hydrogel flowers could fade and rebloom reversibly in response to external stimuli. This work presents a strategy to develop superstructures in hydrogels and sheds light on designing biomimetic materials with intricately architectural superstructure.

High modulus, toughness, and fatigue resistance are usually difficult to be obtained simultaneously in rubbery materials. Here, we report that by superimposing the nanophase separation structure in double network (DN) elastomers using immiscible polymers, the modulus, fracture energy, and energy release rate of fatigue threshold are enhanced all together by 13, 5, and 5 times, respectively. We reveal that the interplay between the DN structure and the nanophase separation structure brings two effects synergistically: (1) formation of nanoclusters overstresses and homogenizes the sacrificial network, thereby remarkably increasing the modulus and yielding stress and (2) the nanoclusters act as viscoelastic nanofillers dissipating energy and pinning the crack propagation, thereby significantly enhancing toughness and fatigue resistance. This work provides a facile approach to superimpose high-order structures in DN materials for excellent mechanical performance. The clarified synergetic effects should be universal for DN materials made of immiscible polymers. We believe that this work will facilitate more studies on elastomers and gels along this line.

Macromolecular crowding (MMC) in cells is a hot topic in biology; therefore, well-characterized measurement standards for the evaluation of the nano-environment in MMC solutions are necessary. We propose to use polarization-dependent fluorescence correlation spectroscopy (Pol-FCS) for evaluation of macromolecular crowding in solutions. Pol-FCS can simultaneously measure the relaxation times of rotational and translational diffusion of fluorescent molecules at the same position, even in living cells with low damage. In this report, the differences in the nano-environment among solutions of small molecules, gels, and MMC solutions were evaluated by comparing their rotational and translational diffusion using Pol-FCS. Moreover, this method could distinguish the phase shift in the polyethylene glycol solution. Finally, we separately evaluated the nano-environment in the cytosol and nucleus of living cells in different cell lines and cell cycles. We expect this evaluation method to be useful in characterizing the nano-environment in MMC studies. In addition, the proposed method may be useful for other nano-environments such as liquid–liquid phase separation.

The fracture of highly deformable soft materials is of great practical importance in a wide range of technological applications, emerging in fields such as soft robotics, stretchable electronics and tissue engineering. From a basic physics perspective, the failure of these materials poses fundamental challenges due to the strongly nonlinear and dissipative deformation involved. In this review, we discuss the physics of cracks in soft materials and highlight two length scales that characterize the strongly nonlinear elastic and dissipation zones near crack tips in such materials. We discuss physical processes, theoretical concepts and mathematical results that elucidate the nature of the two length scales, and show that the two length scales can classify a wide range of materials. The emerging multi-scale physical picture outlines the theoretical ingredients required for the development of predictive theories of the fracture soft materials. We conclude by listing open challenges and future investigation directions., An invited review article, 36 pages, 7 figures

The tough and self-healing hydrogels composed of polyampholytes (PA gels) are drawing great attention due to their multiscale structures and the resultant multiple mechanical properties. This work studies the stress relaxation behavior of PA gels and reveals the underlying multiscale structure evolutions by combining birefringence and small-angle X-ray scattering measurements. The PA gels show a fast and strong stress relaxation that obeys the stress-optical rule, which could be associated with relaxation of chain segment orientation by the breaking of ionic bonds. A slow and weak relaxation of phase structure (∼100 nm) is also observed, which tells that the stress redistributes and local strain amplification gradually builds in the phase network at long relaxation times as a result of synergetic breaking of multiple ionic bonds. This work gives insight into exploring the formation of the crack precursor that is important in the fracture and fatigue of self-healing hydrogels.

Tough hydrogels with facile processability to reform into various shapes are required in many practical applications. In this work, we reported that a novel, tough, and self-healing physical hydrogel based on polyion complex (PIC) can be dissolved in 4 M NaCl solution to form a PIC solution. The PIC solution can be easily reprocessed into various shapes, such as thin films, sheets, fibers, and capsules, by using simple methods, such as casting and injection, while maintaining excellent mechanical properties comparable to, or even better than, the original hydrogel. The reprocessability and robust mechanical properties of PIC hydrogels are promising for practical applications in soft materials, especially in 3D/4D printing technology.

To investigate the effect of inhomogeneity in the first network on the enormously high toughness of double network (DN) gels, we fabricated DN gels with a nearly homogeneous first network structure (named St-TPEG/PAAm DN gels) based on tetra-PEG (TPEG) gels via a molecular stent method. The St-TPEG/PAAm DN gels also show excellent mechanical properties and yielding-like phenomena comparable to conventional DN gels. This result demonstrates that the inhomogeneity within the first network is not essential for the specific toughening mechanism of DN gels. On the other hand, the St-TPEG/PAAm DN gels and conventional DN gels undergo substantially different fracture processes before the yielding point. This suggests the importance of a “homogenization process” for the yielding of DN gels. Since the St-TPEG/PAAm DN gels consist of a well-defined first network, they may serve as model DN gels in the future for further studies on fracture processes of DN gels.

A tough and ductile, ultrathin film, double-network (DN), biopolymer-based hydrogel displaying the yielding phenomenon was synthesized from methacrylated chondroitin sulfate (MCS) and polyacrylamide (PAAm). The DN of MCS/PAAm exhibited a failure stress more than 20 times greater than the single network (SN) of either MCS or PAAm and exhibited yielding stresses over 1500 kPa. In addition, the stress–strain behavior with a yielding region was also seen in a hydrogel of MCS and poly(N,N-dimethyl acrylamide) (PDMAAm). By replacing PAAm with PDMAAm, interactions known to toughen networks are removed. This demonstration supports the idea that the brittle/ductile combination is key to the DN effect over specific interactions between the networks. The MCS/PAAm and MCS/PDMAAm DN hydrogels had comparable mechanical properties to the archtypal DN hydrogels of poly(2-acrylamido-2-methylpropanesulfonic acid) (PAMPS)/PAAm. In addition, these tough and ductile, biopolymer-based, double-network hydrogels demonstrated a s...

Applying the double network principle to develop tough hydrogels with different polymer chemistries is important for the potential application of hydrogel materials. Synthesis of the two interpenetrated networks with contrasting structure and properties required for double networks usually involves a two-step polymerization process. In this work, we present a new method to synthesize tough double network hydrogels by post-physical crosslinking of linear semi-rigid polyelectrolytes entrapped in a chemically crosslinked neutral network. Owing to their semi-rigid structure, the linear polyelectrolytes form a brittle physical network above their overlap concentration in multi-valent ZrCl2O ion solutions without macroscopic phase separation within the flexible neutral network. The double network hydrogels thus prepared exhibit high modulus (∼1.7 MPa), strength (∼1.3 MPa), fracture strain (∼7.3), and strain energy density (∼5.9 MJ m-3), while containing over 80% water. These materials also exhibit modest self-healing ability (∼51% after 30 minutes), demonstrating an additional benefit of a physical sacrificial network. This method is simpler than the conventional two-step polymerization and could be applied to develop tough hydrogels from rigid polyelectrolytes, including biopolymers such as DNA, HA, and chondroitin sulfate.

The high water content of hydrogels makes them important as synthetic biomaterials, and tuning the mechanical properties of hydrogels to match those of natural tissues without changing chemistry is usually difficult. In this study, we have developed a series of hydrogels with varied stiffness, strength, and toughness based on a combination of poly(2-acrylamido-2-methylpropane sulfonic acid) (PAMPS), a strong acidic polyelectrolyte, and poly-N-(carboxymethyl)-N,N-dimethyl-2-(methacryloyloxy) ethanaminium) (PCDME), a polyzwitterion with a weak acidic moiety. We demonstrate that modifying the true molar ratio, R, of PCDME to PAMPS results in four unique categories of hydrogels with different swelling ratios and Young's moduli. When R 6.5, a tough and stiff double-network gel (DN) is formed. Both the PEC and DN gels exhibit high toughness and fracture stress, up to 1.8 and 1.5 MPa, respectively. Importantly, the PEC gels exhibit strong recovery properties along with high toughness, distinguishing them from DN gels. Without requiring a change in chemistry, we can tune the mechanical response of hydrogels over a wide spectrum, making this a useful system of soft and hydrated biomaterials.

Supermacroporous hydrogels, possessing sponge-like structure and permeability, have drawn significant atten-tion for their bioengineering and biomedical applications. However, their mechanical weakness due to their low-density structure is one of their biggest limitations. This work reports a multi-step cryogelation technique, which does not require special equipment, for preparing tough supermacroporous hydrogels on the basis of the double-network (DN) strategy. The produced supermacroporous DN gels possess interconnected pores with pore sizes of 50–230 μm. They also show a com-pressive modulus of up to ~100 kPa, which is 2- to 4-times higher than that of the corresponding supermacroporous single-network (SN) gels, and compressive strength of up to 1 MPa at 80% compression. The supermacroporous DN cryogels are also stretchable with a work of extension of up to 38 kJ m-3, which is 1 to 2 orders larger than that of the SN cryogels. The high stiffness and stretchability distinguish them from other types of cryogels. Supermacroporous triple-network (TN) gels and DN gels composed of different polymer combinations are also prepared. The technique presented herein is suitable for pre-paring supermacroporous DN gels from various polymers; hence, it is promising in meeting bioengineering and biomedical demands.

Quantitative characterization of the energy dissipation zone around a crack tip is the focal point in the fracture mechanics of soft materials. In this report, we present a mechanochemical technique for the visualization and quantification of the degree of polymer strand scission in the damage zone of tough double-network hydrogels. This technique uses mechanoradicals generated by covalent bond scission to initiate radical polymerization, which records the internal fracturing around the crack tip during crack opening or propagation. We adopted the mechanoradical polymerization of N-isopropylacrylamide, which forms a thermoresponsive polymer and whose distribution was visualized using an environment-responsive fluorescent probe. Twoand three-dimensional damage distributions were captured using a laser scanning confocal microscope. This technique also allowed for the quantitative estimation of the spatial distribution of stress, strain, and energy dissipation around the crack tip. The advantages and limitations of this technique are also discussed.

We previously demonstrated that a synthetic negatively charged poly(2-acrylamido-2-methylpropanesulfonic acid) (PAMPS) gel induced chondrogenic differentiation of ATDC5 cells. In this study, we clarified the underlying molecular mechanism, in particular, focusing on the events that occurred at the interface between the gel and the cells. Gene expression profiling revealed that the expression of extracellular components was enhanced in the ATDC5 cells that were cultured on the PAMPS gel, suggesting that extracellular proteins secreted from the ATDC5 cells might be adsorbed in the PAMPS gel, thereby contributing to the induction of chondrogenic differentiation. Therefore, we created "Treated-PAMPS gel," which adsorbed various proteins secreted from the cultured ATDC5 cells during 7 days. Proteomic analysis identified 27 proteins, including extracellular matrix proteins such as Types I, III, and V collagens and thrombospondin (THBS) in the Treated-PAMPS gel. The Treated-PAMPS gel preferentially induced expression of chondrogenic markers, namely, aggrecan and Type II collagen, in the ATDC5 cells compared with the untreated PAMPS gel. Addition of recombinant THBS1 to the ATDC5 cells significantly enhanced the PAMPS-induced chondrogenic differentiation, whereas knockdown of THBS1 completely abolished this response. In conclusion, we demonstrated that the PAMPS gel has the potential to induce chondrogenic differentiation through novel reservoir functions, and the adsorbed THBS plays a significant role in the induction.

Inspired by bone tissues, we mineralized low crystalline hydroxyapatite (HAp) particles in double network (DN) hydrogels, and we observed that the HAp minerals toughen the gels. The contribution of dissipated energy from HAp minerals was over 500% higher than that from the polymer during tensile deformation. We elucidated that the amorphous parts in the HAp minerals break at deformation, acting as energy-dissipative sacrificial bonds. This result implies that not only brittle polymer networks but also minerals can provide sacrificial bonds to toughen soft materials.

Polyampholyte hydrogels (PA gels) are drawing great attention for their excellent mechanical properties including self-healing, high toughness, and fatigue resistance. These mechanical performances...

Polyelectrolyte gels exhibit intrinsic salt-sensitive swelling behaviour, which causes size instability in ionic environments. Thus, polyelectrolyte gels that show salt-insensitive swelling have been anticipated for applications in ionic environments, such as medical materials used in vivo. We found that double-network (DN) gels consisting of both a polyelectrolyte network and a non-ionic network are resistant to salt-sensitive swelling. This resistance is attributed to their lower osmotic pressure originating from mobile ions relative to the osmotic pressure of mixing at swelling equilibrium. Our investigation indicated that the two contrasting network structures within the DN gels are vital for achieving these properties, where the structures include a highly prestretched and sparse polyelectrolyte network and a coiled and dense non-ionic network. The salt-insensitivity of the DN gels will lead to their unique applications in ionic environments.

We report a method to create anisotropic double-network (DN) hydrogels, through the controlled orientation of a physical sacrificial network. A cross-linked polyacrylamide hydrogel is synthesized from a solution containing a semirigid anionic polyelectrolyte. Subsequently, the gel is stretched to orient the semirigid polyelectrolyte, which does not relax in the stretched state because of the high contour length in comparison to the mesh size of the polyacrylamide network. The polyelectrolyte is then physically cross-linked with a multivalent cation, ZrCl2O, to fix the anisotropy. Anisotropy was visualized by observing birefringence and quantified by small-angle X-ray scattering. By comparing the scattering in the oriented direction versus perpendicular to the oriented direction, a structural anisotropy factor was calculated. Uniaxial tensile testing was performed on samples of varying prestretch, both parallel and perpendicular to the stretching direction. Young's modulus, fracture stress, fracture strain, and work of extension were characterized, and the resulting mechanical anisotropy was compared to the structural anisotropy factor. We find that the anisotropy of Young's modulus and fracture stress is directly controlled by the anisotropy of the sacrificial network, while fracture strain and work of extension show little influence from structural anisotropy. The results of this work demonstrate that prestretching of a physical sacrificial network is a controllable and simple method to create anisotropic DN hydrogels.

Since the birth of synthetic hydrogel 60 years ago, hydrogels possessing various useful properties and functions have been developed. The research directions of hydrogels have expanded to diverse application fields as well. However, in contrast to natural hydrogels found in biological soft tissues, which have elaborate structures from molecular to macroscopic scales and sophisticated functions, synthetic hydrogels only have very simple structures and naive functions. We have great opportunities to develop hydrogel materials through learning from nature. This Perspective discusses the opportunities and challenges in the fabrication of hydrogels with excellent physical functions by mimicking biological structures at different length scales.

Recently, we have developed a hydroxyapatite (HAp)-hybridized double-network (DN) hydrogel (HAp/DN gel), which can robustly bond to the bone tissue in the living body. The purpose of this study is to clarify whether the HAp/DN gel surface can differentiate the bone marrow-derived mesenchymal stem cells (MSCs) to osteogenic cells. We used the MSCs which were harvested from the rabbit bone marrow and cultured on the polystyrene (PS) dish using the autogenous serum-supplemented medium. First, we confirmed the properties of MSCs by evaluating colony forming unit capacity, expression of MSC markers using flow cytometry, and multidifferential capacity. Secondly, polymerase chain reaction analysis demonstrated that the HAp/DN gel surface significantly enhanced mRNA expression of the eight osteogenic markers (TGF-β1, BMP-2, Runx2, Col-1, ALP, OPN, BSP, and OCN) in the cultured MSCs at 7 days than the PS surfaces (p < 0.0001), while the DN gel and HAp surfaces provided no or only a slight effect on the expression of these markers except for Runx2. Additionally, the alkaline phosphatase activity was significantly higher in the cells cultured on the HAp/DN gel surface than in the other three material surfaces (p < 0.0001). Thirdly, when the HAp/DN gel plug was implanted into the rabbit bone marrow, MSC marker-positive cells were recruited in the tissue generated around the plug at 3 days, and Runx2 and OCN were highly expressed in these cells. In conclusion, this study demonstrated that the HAp/DN gel surface can differentiate the MSCs into osteogenic cells.

Hydrogels are promising materials for several applications, including cell scaffolds and artificial load-bearing substitutes (cartilages, ligaments, tendons, etc.). Direct observation of the nanoscale polymer network of hydrogels is essential in understanding its properties. However, imaging of individual network strands at the molecular level is not achieved yet due to the lack of suitable methods. Herein, for the first time, we developed a novel mineral-staining method and network fixation method for transmission electron microscopy observation to visualize the hydrogel network in its unperturbed conformation with nanometer resolution. Surface network observation indicates that the length of surface dangling chains, which play a major role in friction and wetting, can be estimated from the gel mesh size. Moreover, bulk observations reveals a hierarchical formation mechanism of gel heterogeneity. These observations have the great potential to advance gel science by providing comprehensive perspective that link bulk gel properties with nanoscale.

Double network hydrogels (DN gels) exhibit extraordinarily high strength and toughness by interplay of the two contrasting networks: the rigid, brittle network serves as a sacrificial bond that fractures at a relatively low strain, while the soft, stretchable network serves as hidden length that sustains stress by large extension afterward. The internal fracture process of the brittle network strongly depends on the relative strength of the two networks. In this study, we study the internal fracturing process of typical DN gels that show yielding or necking under uniaxial stretching using in situ small-angle X-ray scattering. Two samples consisting of the same brittle first network from poly(2-acrylamido-2-methylpropanesulfonic acid) but stretchable second network from poly(N,N-dimethylacrylamide) of different concentrations were adopted. We found that (1) the brittle network shows nonaffine deformation even far below the yield strain by local fracture; (2) for the sample of low second network concentration, significant strain amplification occurs around the submicrometer-scale voids (defects) preexisting in the brittle network, which induces the fracture percolation of brittle network from voids to show the necking phenomenon; and (3) the strain amplification at voids is suppressed in the sample of high second network concentration, and fracture of brittle network occurs dispersedly, showing yielding without necking.

Recent studies reported a multiscale structure in tough and self-healing hydrogels containing physical associations. For example, a type of tough and self-healing hydrogel from charge-balanced polyampholytes (PA) has a mesoscale bicontinuous double network structure with structural length around 400 nm. This mesoscale network structure plays an essential role in the multistep rupture process, which leads to the high toughness of PA hydrogels. In this work, by using an osmotic stress method, we symmetrically studied how the relative strength of soft and hard networks and the strength of ionic bonds influence the property of PA gels. We found that increasing osmotic stress of the bath solution triggers the structure transition from bicontinuous double network structure to a homogeneous structure, which drives the concurrently opaque−transparent transition in optical property and viscoelastic−glassy transition in mechanical behavior. The gels around the structural transition point were found to possess both high toughness (fracture energy of 7200 J m−2) and high stiffness (Young’s modulus of 12.9 MPa), which is a synergy of soft network and hard network of the bicontinuous structure. Our work not only provides an approach to tune the structure and property of physical hydrogels through tuning physical association but also gives a demo to investigate their relationships, yet another step forward gives inspiration to design a new type of tough and self-healing materials around the structural transition point.

The double network concept, based on the fracture of sacrificial bonds, has been revolutionary toward the creation of robust soft materials. Based on the essence of double network hydrogels, macroscale, three-dimensional printed rigid sacrificial networks are embedded within silicone rubber stretchable matrices. Preferential fracture of the sacrificial network results in a , similar to 60 time increase in stiffness and a similar to 50% increase in the work of extension compared with the neat matrix. Maximizing yield strength while maintaining multistep internal fracture occurs when the strength of the sacrificial network approaches the strength of the matrix. Upon determining the optimal sacrificial network strength, the sacrificial bond section density can be increased to maximize energy dissipation and toughening efficiencies up to similar to 70% of the maximum theoretical toughness are achieved. High toughness and dissipation are achieved because topological interlocking enables significant force transmission to the sacrificial network at smaller length scales than interfacial adhesion, allowing much higher sacrificial bond density. This method is general and can be used with a variety of materials systems, without requiring strong interfacial adhesion, contrasting traditional composite systems. Demonstrating that the double network concept can be used at length scales far beyond the molecular scale will have important implications toward the development of future structural materials.

Double-network (DN) hydrogels have attracted considerable attention owing to their unique mechanism to show extraordinary mechanical strength and toughness. Although the toughening mechanism of the...

The human body is composed of composite structures made of water-rich hydrophilic domains and hydrophobic barriers. Combining hydrogels with elastomers results in similar synthetic biomaterials applicable to fields ranging from stretchable electronics to actuators. Here, we report a method to combine hydrogels with elastomers via a glass fiber fabric interphase. The interphase plays two roles: it enables chemically different materials to be robustly bound without chemical treatment while also dramatically improving the mechanical properties of the composite. Maximum interfacial adhesion energies of similar to 1,000 N m(-1) between the hydrogel and fabric and similar to 360 N m(-1) between the elastomer and fabric approach adhesion values of chemically bound soft materials. The composite tearing toughness (143 kJ m(-2)) vastly exceeds that of all neat components. In these materials, Young's modulus is high (similar to 1.2 GPa), while bending modulus is low (similar to 7 MPa), resulting in structures that can serve as actuators through controlled solvent exposure.

The hydrogel chemical structure at the gel-solution interface is important toward practical use, especially in tough double network (DN) hydrogels that have promising applications as structural biomaterials. In this work, we regulate the surface chemical structure of DN hydrogels and the surface–bulk transition by the molding substrate used for the synthesis of the second network. To characterize the surface and bulk structure, we combined attenuated total reflectance Fourier-transform infrared spectroscopy and a newly developed microelectrode technique that probe the electric potential distribution within a hydrogel. We found that the polymerization on a repulsive substrate leads to the formation of a thin layer of a second network on the surface of DN hydrogels, which makes the surface different from the bulk. By controlling the second network polymerization conditions and molding substrate, the surface–bulk transition region can be regulated, so that either only the second network or both networks are present at the DN hydrogel surface. Through these findings, we gained a new insight into the structure formation at the DN hydrogel surface, and this leads to easy regulation of the hydrogel surface structure and properties.

The incorporation of a stiff and brittle phase into a soft and flexible polymer network makes double network hydrogels remarkably tougher than the conventional one. It also induces a stress softeni...

Fiber reinforced soft composites (FRSCs) have been developed recently by combining tough but soft polyampholyte hydrogels with stiff yet flexible woven glass fabrics. In this work, we find that the soft composites show increased tearing resistance with sample size and achieve size-independent, exceptionally high tearing energy above a specific size on the centimeter scale. Such size-dependent tearing behavior correlates with the failure mode change from fiber pull-out to fiber fracture. These findings demonstrate that the rigid fibers in the soft matrices transmit force over a large distance, giving the composites very large process zones. Tremendous energy is dissipated in the large process zones, resulting in the superior fracture resistance of FRSCs. By saturation of the process zone size, the soft composites become extraordinarily tough, showing an intrinsic tearing energy of ~1000 kJ m−2 that outperforms other existing tough materials. These novel FRSC materials from hydrated biocompatible hydrogels fill the gap between soft materials and traditional rigid materials, as demonstrated by their high tensile modulus (several GPa) and strength (> 300 MPa), along with exceptionally high tearing toughness.

The double-network (DN) structure is a state-of-the-art strategy used for toughening soft materials. The challenge for widespread applications, however, is the difficulty in synthesizing the two in...

When a poroelastic gel is released from a patterned mold, surface stress drives deformation and solvent migration in the gel and flattens its surface profile in a time-dependent manner. Specifically, the gel behaves like an incompressible solid immediately after removal from the mold, and becomes compressible as the solvent is able to squeeze out of the polymer network. In this work, we use the finite element method (FEM) to simulate this transient surface flattening process. We assume that the surface stress is isotropic and constant, the polymer network is linearly elastic and isotropic, and that solvent flow obeys Darcy's law. The short-time and long-time surface profiles can be used to determine the surface stress and drained Poisson's ratio of the gel. Our analysis shows that the drained Poisson's ratio and the diffusivity of the gel can be obtained using interferometry and high-speed video microscopy, without mechanical measurement.

Soft and wet hydrogels have many similarities to biological tissues, though their mechanical fragility had been one of the biggest obstacles in biomedical applications. Studies and developments in double network (DN) hydrogels have elucidated how to create tough gels universally based on sacrificial bond principles and opened a path for biomedical application of hydrogels in regenerative medicine and artificial soft connective tissues, such as cartilage, tendon, and ligament, which endure high tension and compression. This review explores a universal toughening mechanism for and biomedical studies of DN hydrogels. Moreover, because the term sacrificial bonds has been mentioned often in studies of bone tissues, consisting of biomacromolecules and biominerals, recent studies of gel–biomineral composites to understand early-stage osteogenesis and to simulate bony sacrificial bonds are also summarized.

The utility and lifetime of materials made from polymer networks, including hydrogels, depend on their capacity to stretch and resist tearing. In gels and elastomers, those mechanical properties are often limited by the covalent chemical structure of the polymer strands between cross-links, which is typically fixed during the material synthesis. Here, we report polymer networks in which the constituent strands lengthen through force-coupled reactions that are triggered as the strands reach their nominal breaking point. Reactive strand extensions of up to 40% lead to hydrogels that stretch 40-50% further than, and exhibit tear energies twice that of, networks made from analogous control strands. The enhancements are synergistic with those provided by double network architectures, and complement other existing toughening strategies.

The double network (DN) gel is a rigid, tough, and safe hydrogel; however, like all hydrogels and existing particle embolization materials composed of a polymer, they lack X-ray visibility. Thus, it is not possible to locate the embolization material in the body. In this study, we successfully developed an X-ray-visible embolization material, a tough DN gel incorporated with biocompatible heavy metal powder. The DN gel particles, composed of poly(N,N'-dimethylacrylamide) and poly(2-acrylamido-2-methylpropanesulfonic acid) with tantalum powder, were synthesized via two-step suspension radical polymerization. The characteristics of the DN particles were evaluated by comparing them with Embosphere®, an existing embolization material. Furthermore, we used a rat carotid artery embolic model to evaluate the material’s X-ray computed tomography visibility in vivo. The developed embolization material was visible in X-ray computed tomography scans and safe for use in the body. Moreover, as it remained in the vessels for a long time, it is expected to be more effective than Embosphere®. Thus, the developed material is a promising DN particle embolization material with X-ray computed tomography visibility.

The surface of soft solids carries a surface stress that tends to flatten surface profiles. For example, surface features on a soft solid, fabricated by moulding against a stiff-patterned substrate, tend to flatten upon removal from the mould. In this work, we derive a transfer function in an explicit form that, given any initial surface profile, shows how to compute the shape of the corresponding flattened profile. We provide analytical results for several applications including flattening of one-dimensional and two-dimensional periodic structures, qualitative changes to the surface roughness spectrum, and how that strongly influences adhesion.

In this paper, the frictional behavior of a neutral hydrogel, polyvinyl alcohol (PVA), on smooth solid substrates with various levels of hydrophobicity have been investigated in water using a strain-controlled parallel-plate rheometer. For the sliding velocity dependence of friction, we detected a distinct friction transition on hydrophobic substrates that are strongly adhesive to the gel, while no clear transition was observed on hydrophilic substrates that are weakly adhesive to the gel. Even on the most hydrophobic substrate, the maximum frictional stress is approximately 1/10–1/5 of the gel’s elastic modulus under a large normal strain of 26%. Furthermore, the frictional stress on hydrophobic substrates in the high velocity region, larger than the transition, is much lower than that on hydrophilic ones. We attempted to explain these phenomena with the help of two models: a molecular model based on the thermal fluctuations occurring during adsorption–desorption of polymers and a continuum mechanics model based on elastic dewetting and forced wetting.

Double-network (DN) gels, consisting of brittle first and ductile second networks, possess extraordinary strength, extensibility, and fracture toughness while maintaining a high solvent content. Herein, we prepare DN gels consisting of various concentrations of the first and second networks to investigate the effect of each network structure on the tensile and fracture properties of DN gels. The results showed that the tensile properties of DN gels before yielding are mainly dominated by the first network, serving as a skeleton, whereas the properties after necking are determined by both networks. Moreover, we found that the DN gels with significant energy dissipation capacities exhibit high fracture resistance. Thus, this study not only confirms the factors determining the mechanical characteristics of DN gels but also explains how the two networks concertedly improve the toughness of DN gels.

Polyampholyte (PA) hydrogels are a fascinating class of soft materials that can exhibit high toughness while retaining self-healing characteristics. This behavior results from the random distribution of oppositely charged monomers along the polymer chains that form transient bonds with a range of bond strengths. PAs can be dissolved in aqueous salt solutions and then recast via immersion precipitation, making them particularly useful as surface coatings in biomedical applications. Moreover, this immersion precipitation technique allows these PA hydrogels to be fabricated into films less than 100 nm. One critical challenge to this aqueous processing method is the recrystallization of the salt upon water evaporation. Such recrystallization can disrupt the hydrogel morphology especially in thin films. In this study, a deep eutectic solvent (DES) formed from urea and choline chloride was used to dissolve PAs made from p-styrenesulfonic acid sodium salt and 3-(methacryloylamino)propyl trimethylammonium chloride. This DES has a freezing point of 12 degrees C, allowing it to remain stable and liquid-like at room temperatures. Thus, these PAs can be processed in DES solutions, without this issue of recrystallization and with simple methods such as spin coating and dip coating. These methods allow these hydrogels to be used in thin (

Biological connective tissues, such as cartilage and corneal stroma, are essentially hydrogels consisting of fibrous collagen and proteoglycans. Little is known of the surface properties of the hydrogel, although we observe fascinating tribological behavior in biological soft tissues, such as extremely low friction between animal cartilages. We consider that the role of the solvated polymer network existing in the extracellular matrix as a gel state is critically important in the specific frictional behavior of cartilages. In order to elucidate the general tribological features of a solvated polymer matrix, the friction of various kinds of hydrogels has been investigated, and very rich and complex frictional behaviors are observed. The friction force and its dependence on the load differ with the chemical structure of the gels, surface properties of the opposing substrates, and the measurement conditions, which are totally different from those of solids. Most importantly, the coefficient of friction of gels, μ, varies over a wide range and exhibits very low values (μ ≈ 10−3–10−4), which cannot be obtained from the friction between two solid materials. A repulsion–adsorption model has been proposed to explain the gel friction, which says that the friction is due to lubrication of a hydrated layer of polymer chains when the polymer chain of the gel is non-adhesive (repulsive) to the substrate, and the friction is due to elastic deformation of the adsorbed polymer chain when it is adhesive to the substrate.

Quantitative characterization of the energy dissipative zone around the crack tip is the central issue in fracture mechanics of soft materials. In this research, we present a mechanochemical technique to visualize the bond scission of the first network in the damage zone of tough double-network hydrogels. The mechanoradicals generated by polymer chain scission are employed to initiate polymerization of a thermoresponsive polymer, which is visualized by a fluorophore. This technique records the spatial distribution of internal fracturing from the fractured surface to the bulk, which provides the spatial profiles of stress, strain, and energy dissipation around the crack-tip. The characterized results suggest that, in addition to the dissipation in relatively narrow yielded zone which is mostly focused in the previous works, the dissipation in wide pre-yielding zone and the intrinsic fracture energy have also significant contribution to the fracture energy of a DN gel.

Anisotropy of strain-induced internal damage in tough double network (DN) hydrogels is characterized by a sequence of two tensile experiments. Firstly, the virgin DN gels are subjected to a single biaxial loading-unloading cycle using various combinations of the two maximum strains λx,m and λy,m in the x- and y-directions (λx,m ≥ λy,m). Secondly, the rectangular subsamples, which are cut out from the unloaded specimens so that the long axis can have an angle (θ) relative to the larger pre-strain (x-)axis, are stretched uniaxially along the long axis. Directional internal damage caused by various types of pre-stretching is evaluated by comparing the loading curves of the virgin gels and the subsamples with various θ. The modulus reduction (ΔEθ) and strain-energy reduction (Dθ) are characterized as functions of λx,m, λy,m and θ. The anisotropy of damage increases with the anisotropy of imposed pre-strain field as well as λx,m, which is also observed in the anisotropic re-swelling behavior of the subsamples. The damage and the extensibility of the subsamples with θ = 0° increase with λy,m, and the damage of the subsamples with θ = 90° significantly increases with λx,m. These results reveal the presence of a pronounced damage cross-effect: a finite portion of the chain fractures in the first brittle network in one direction is caused by loading in the other orthogonal direction. This feature is in contrast to the very modest damage cross-effect in the silica reinforced elastomers, which show apparently similar stress-softening behavior but with a different origin. The strong damage cross-effect is a key feature of the internal fracture mechanism of the tough DN gels.

Polyelectrolyte complexation between oppositely charged polyelectrolytes forms coacervates in dilute solutions and thin films in concentrated solutions. It is difficult to obtain macroscopically uniform bulk polyelectrolyte complex (PEC) materials, since the two polymers form insoluble complexes quickly at the contact interface during mixing, resulting in heterogeneous aggregates. Here, we succeeded in preparing bulk PEC materials based on desalting-induced polyelectrolyte complexation via viscoelastic phase separation. With a high ionic strength aqueous medium, a homogeneous and concentrated solution containing oppositely charged polyelectrolytes is prepared. Desalting of the counter-ions and co-ions of the solution through semi-permeable membranes induces viscoelastic phase separation of the solution to form a physical hydrogel with open pore structure. Regulating the charge ratio of the two oppositely charged polymers results in significant changes in the porous morphology and mechanical properties. The charge-balanced PEC hydrogels show unique properties including high toughness and self-recovery due to the reversible ionic associations. The porous yet tough properties of bulk PEC hydrogels makes them potential candidates for applications such as cell scaffolds.