High‐Performance Flexible Sensors of Self‐Healing,Reversibly Adhesive,and Stretchable Hydrogels for Monitoring Large and Subtle Strains

Flexible sensors are becoming required in heath monitoring and human–machine interfaces, but it is still a challenge to develop flexible sensors with integrated high performances. Herein, high‐performance flexible sensors are fabricated that are self‐healing, reversibly adhesive, and utilizing stretchable hydrogels, which are composed of a pluronic F127 diacrylate (F127DA) cross‐linked poly(acrylic acid) (PAA) network and polydopamine (PDA), and further cross‐linked by Fe³⁺. The unique structure endows the resulting hydrogels (PAA‐PDA‐Fe³⁺ hydrogels) excellent self‐healing property, reversible adhesion property, mechanical stretchability, and electrical conductivity. On the basis of the excellent properties of PAA‐PDA‐Fe³⁺ hydrogels, flexible sensors with large sensing range (0–575%), high sensitivity (GF = 6.31), low response time (0.25 s), and excellent robustness (>500 cycles) are assembled and further applied in detecting both large and subtle strains induced by human motions and water ripple. Overall, this work not only provides an alternative clue to construct multi‐functional hydrogels, but also offers a new kind of high‐performance materials for flexible electronic devices, especially those for health monitoring and human–machine interface.     

Synthesis of multifunctional high strength,highly swellable,stretchable and self‐healable pH‐responsive ionic double network hydrogels

The multifunctional double network (DN) soft hydrogels reported here are highly swellable and stretchable pH‐responsive smart hydrogel materials with sufficient strength and self‐healing properties. Such multifunctional hydrogels are achieved using double crosslinking structures with multiple physical and chemical crosslinks. They consist of a copolymer network of acrylamide (AM) and sodium acrylate (Na‐AA) and other reversible network of poly(vinyl alcohol)–borax complex. They were characterized by Fourier transform IR analysis and studied for their hydrogen bonding and ionic interaction. The degree of equilibrium swelling was observed to be as high as 5959% (at pH 7.0) for a hydrogel with AM/Na‐AA = 25/75 wt% in the network (GS‐6 sample). The highest degree of swelling was observed to be 6494% at pH 8.5. The maximum tensile strength was measured to be 1670, 580 and 130 kPa for a DN hydrogel (GS‐2 sample: AM/Na‐AA =75/25 wt% with 20, 40 and 60 wt% water content, respectively). The self‐healing efficiency was estimated to be 69% for such a hydrogel. These multifunctional DN hydrogels with amalgamation of many functional properties are unique in hydrogel materials and such materials may find applications in sensors, actuators, smart windows and biomedical applications. © 2018 Society of Chemical Industry     

Highly Stretchable,Transparent, and Bio‐Friendly Strain Sensor Based on Self‐Recovery Ionic‐Covalent Hydrogels for Human Motion Monitoring

Stretchable, flexible, and strain‐sensitive hydrogels have gained tremendous attention due to their potential application in health monitoring devices and artificial intelligence. Nevertheless, it is still a huge challenge to develop an integrated strain sensor with excellent mechanical properties, broad sensing range, high transparency, biocompatibility, and self‐recovery. Herein, a simple paradigm of stretchable strain sensor based on multifunctional hydrogels is prepared by constructing synergistic effects among polyacrylamide (PAM), biocompatible macromolecule sodium alginate (SA), and Ca ion in covalently and ionically crosslinked networks. Under large deformation, the dynamic SA‐Ca²⁺ bonds effectively dissipate energy, serving as sacrificial bonds, while the PAM chains bridge the crack and stabilize the network, endowing hydrogels with outstanding mechanical performances, for instance, high stretchability and compressibility, as well as excellent self‐recovery performance. The hydrogel is assembled to be a transparent and wearable strain sensor, which has good sensitivity and very wide sensing range (0–1700%), and can precisely detect dynamic strains, including both low and high strains (20–800% strain). It also exhibits fast response time (800 ms) and long‐time stability (200 cycles). The sensor can monitor and distinguish complicated human motions, opening up a new route for broad potential applications of eco‐friendly flexible strain‐sensing devices.     

Super Bulk and Interfacial Toughness of Amylopectin Reinforced PAAm/PVA Double‐Network Hydrogels via Multiple Hydrogen Bonds

A simple, multiple‐hydrogen‐bond approach to fabricating physically crosslinked, Amylopectin reinforced polyacrylamide/poly(vinyl alcohol) (Amy/PAAm/PVA) double‐network (DN) hydrogels with super toughness in bulk and at solid interfaces is reported. The Amy/PAAm/PVA DN hydrogels exhibit high tensile strength (854.1 kPa), high extensibility (≈eight times), high bulk toughness (4094.8 kJ m^?3), good self‐recovery property (≈92% of self‐recovery at room temperature), and strong adhesion to nonporous glass surfaces (≈158 kPa). Such tough and adhesive DN hydrogels have great potential for various applications in engineering artificial soft tissues, flexible electronics, and wearable devices.     

Nanoclay Reinforced Self‐Cross‐Linking Poly(N‐Hydroxyethyl Acrylamide) Hydrogels with Integrated High Performances

Despite recent significant progress in fabricating tough hydrogels, it is still a challenge to realize high strength, large stretchability, high toughness, rapid recoverability, and good self‐healing simultaneously in a single hydrogel. Herein, Laponite reinforced self‐cross‐linking poly(N‐hydroxyethyl acrylamide) (PHEAA) hydrogels (i.e., PHEAA/Laponite nanocomposite [NC] gels) with dual physically cross‐linked network structures, where PHEAA chains can be self‐cross‐linked by themselves and also cross‐linked by Laponite nanoplatelets, demonstrate integrated high performances. At optimal conditions, PHEAA/Laponite NC gels exhibit high tensile strength of 1.31 MPa, ultrahigh tensile strain of 52.23 mm mm^?1, high toughness of 2238 J m^?2, rapid self‐recoverability (toughness recovery of 79% and stiffness recovery of 74% at room temperature for 2 min recovery without any external stimuli), and good self‐healing properties (strain healing efficiency of 42%). The work provides a promising and simple strategy for the fabrication of dual physically cross‐linked NC gels with integrated high performances, and helps to expand the fundamentals and applications of NC gels.     

Dual Cross‐Linked Hydrogels with High Strength,Toughness, and Rapid Self‐Recovery Using Dynamic Metal–Ligand Interactions

A dual cross‐linking design principle enables access to hydrogels with high strength, toughness, fast self‐recovery, and robust fatigue resistant properties. Imidazole (IMZ) containing random poly(acrylamide‐co‐vinylimidazole) based hydrogels are synthesized in the presence of Ni²⁺ ions with low density of chemical cross‐linking. The IMZ‐Ni²⁺ metal–ligand cross‐links act as sacrificial motifs to effectively dissipate energy during mechanical loading of the hydrogel. The hydrogel mechanical properties can be tuned by varying the mol% of vinylimidazole (VIMZ) in the copolymer and by changing the VIMZ/Ni²⁺ ratio. The resultant metallogels under optimal conditions (15 mol% VIMZ and VIMZ/Ni²⁺ = 2:1) show the best mechanical properties such as high tensile strength (750 kPa) and elastic modulus (190 kPa), combined with high fracture energy (1580 J m^?2) and stretchability (800–900% strain). The hydrogels are pH responsive and the extent of energy dissipation can be drastically reduced by exposure to acidic pH. These hydrogels also exhibit excellent anti‐fatigue properties (complete recovery of dissipated energy within 10 min after ten successive loading–unloading cycles at 400% strain), high compressive strength without fracture (17 MPa at 96% strain), and self‐healing capability due to the reversible dissociation and re‐association of the metal ion mediated cross‐links.     

Synthesis of poly(acrylic acid)–Fe3+/gelatin/poly(vinyl alcohol) triple‐network supramolecular hydrogels with high toughness,high strength and self‐healing properties

Hydrogels with good mechanical and self‐healing properties are of great importance for various applications. Poly(acrylic acid)–Fe³⁺/gelatin/poly(vinyl alcohol) (PAA‐Fe³⁺/Gelatin/PVA) triple‐network supramolecular hydrogels were synthesized by a simple one‐pot method of copolymerization, cooling and freezing/thawing. The PAA‐Fe³⁺/Gelatin/PVA triple‐network hydrogels exhibit superior toughness, strength and recovery capacity compared to single‐ and double‐network hydrogels. The mechanical properties of the synthesized hydrogels could be tailored by adjusting the compositions. The PAA‐Fe³⁺/Gelatin/PVA triple‐network hydrogel with 0.20 mmol Fe³⁺, 3% gelatin and 15% PVA could achieve good mechanical properties, the tensile strength and elongation at break being 239.6 kPa and 12.8 mm mm^?1, respectively, and the compression strength reaching 16.7 MPa under a deformation of about 91.5%. The synthesized PAA‐Fe³⁺/Gelatin/PVA triple‐network hydrogels have good self‐healing properties owing to metal coordination between Fe³⁺ and carboxylic groups, hydrogen bonding between the gelatin chains and hydrogen bonding between the PVA chains. Healed PAA‐Fe³⁺(0.20)/Gelatin3%/PVA15% triple‐network hydrogels sustain a tensile strength of up to 231.4 kPa, which is around 96.6% of the tensile strength of the original samples. Therefore, the synthesized triple‐network supramolecular hydrogels would provide a new strategy for gel research and expand the potential for their application. © 2019 Society of Chemical Industry     

A Bio‐Inspired and Biomass‐Derived Healable Photochromic Material Induced by Hierarchical Structural Design

Utilization of bionics to develop stimuli responsive polymers that can heal damage with excellent restorability is particularly attractive for a sustainable society. Herein, inspired by chameleons, a hierarchical structural design strategy is proposed and illustrated to fabricate a healable photochromic material based on a self‐healable polymeric matrix and a finely dispersed photochromic spirooxazine. The self‐healable polymeric matrix is fabricated via the integration of multiple hydrogen bonds (H bonds) and covalent cross‐links into a biomass‐derived elastomer. The dynamic nature and soft characteristics enable the as‐prepared elastomer superior extensibility as well as self‐healing ability, while the covalent cross‐links can assist the reassociation of ruptured H bonds. The representative elastomer exhibits an extensibility of 2600% and toughness of 42.76 MJ m^?3. Furthermore, it shows good self‐healing ability with complete recovery of scratch as well as restoration against 1900% of elongation and 24.1 MJ m^?3 of toughness after healing at 60 °C for 24 h. This combination of moderate toughness, good self‐healing ability, and smart photochromic property in biomass‐derived materials should largely improve their applicability, reliability, and sustainability in various materials and devices.     

Viscoelastic behaviour of self‐assembling polyurethane and poly(vinyl alcohol)

The rheological behaviour of polyurethane (PU) and poly(vinyl alcohol) (PVA) was investigated in aqueous solution and the hydrogel state. The dependence of viscosity on polymer concentration is discussed. The formation of supramolecular structures induced by temperature increase or shear conditions was evidenced. In PU solutions, as temperature increases, a self‐assembling process occurs due to hydrogen bonding and hydrophobic interactions determining a thermoreversible hydrogel formation. In creep and recovery tests, the weak PU network presents high elasticity only at low shear stress (below 10 Pa); it recovers only 15%–20% of strain above 40 Pa and the hydrogel structure fails at high shear stress (above 150 Pa). Also, PU hydrogel is not able to recover its structure after being submitted to successive low and high deformations. In PVA solutions, a shear induced aggregation was observed at 37 °C. PVA hydrogels obtained by the freezing–thawing method present high elasticity and stability due to the strong polymer–polymer interactions established between the polymer chains. Physical networks based on PU/PVA mixtures synergistically combine the characteristics of the two polymers, showing high elasticity when a shear stress up to 3000 Pa is applied during the creep test followed by a fast recovery of the hydrogel structure after exhibiting successive levels of deformation (self‐healing ability). Therefore, these hydrogels are suitable materials for tissue engineering applications. © 2019 Society of Chemical Industry     

Photo‐Crosslinking Strategy Constructs Adhesive,Superabsorbent, and Tough PVA‐Based Hydrogel through Controlling the Balance of Cohesion and Adhesion

An ideal hydrogel with excellent adhesive performance has drawn much attention in research and applications. In this paper, a photo‐crosslinked polyvinyl alcohol bearing styrylpyridinium group/cellulose nanocrystals (PVA‐SbQ/CNC) composite hydrogel is designed through photo‐crosslinking technology for preventing the physical crosslinking of polyvinyl alcohol to maintain enough hydroxy groups in the hydrogel. Thus, the hydrogel exhibits excellent adhesive behavior not only for various solid substrates (plastics, rubbers, glasses, metals, and woods) but also muscle and fat. In addition, the formation mechanism, the swelling behavior, and mechanical strength are also investigated. Also, these results show that photo‐crosslinked PVA‐SbQ/CNC hydrogel possesses high swelling rate, super stretchability, and high toughness. Moreover, adhesive, mechanical, and swelling properties of PVA‐SbQ/CNC hydrogels can be changed with the increase of total incident light intensity. It is anticipated that the photo‐crosslinked PVA‐SbQ/CNC hydrogel would play a significant role in the applications of wound dressing, medical electrodes, tissue adhesives, portable equipment, and super absorbent materials. In this sense, the simple photo‐crosslinking strategy would provide new ideas for designing soft and adhesive materials through controlling the balance of cohesion and adhesion.     

Novel collagen‐based hydrogels with injectable,self‐healing,wound‐healing properties via a dynamic crosslinking interaction

Collagen‐based hydrogels have gained significant popularity in biomedical applications; however, traditional collagen hydrogels are easily disabled for lack of self‐healing properties due to their non‐reversible bonds. Here, a self‐healing collagen‐based hydrogel has been developed based on dynamic network chemistry, consisting of dynamic imine linkages between collagen and dialdehyde guar gum, as well as diol‐borate ester bonds between guar gum and borax. In addition, macromolecular interactions amongst macromolecules are involved. The above‐mentioned interactions were validated by Fourier transform infrared spectroscopy, sodium dodecyl sulfate polyacrylamide gel electrophoresis and DSC. The as‐prepared collagen‐based hydrogels showed good injectability and rapid self‐healing capacity (within 3 min) as reflected from injection tests, optical microscope observations, rheological measurements, as well as self‐healing studies. In addition, the collagen‐based hydrogels showed accelerated wound‐healing properties. This study offers a facile strategy to endow self‐healing ability on collagen‐based hydrogels without any external stimulus, which show great application potential as wound dressings. © 2020 Society of Chemical Industry     

Highly stretchable,tough, and self‐recoverable and self‐healable dual physically crosslinked hydrogels with synergistic “soft and hard” networks

Strength, toughness and self‐recoverability are among the most important properties of hydrogels for tissue‐engineering applications. Yet, it remains a challenge to achieve these desired properties from the synthesis of a single‐polymer hydrogel. Here, we report our one‐pot, a monomer‐polymerization approach to addressing the challenge by creating dual physically crosslinked hybrid networks, in particular, synergistic “soft and hard” polyacrylic acid‐Fe³⁺ hydrogels (SHPAAc‐Fe³⁺). Favorable mechanical properties achieved from such SHPAAc‐Fe³⁺ hydrogels included high tensile strength (about 1.08 MPa), large elongation at break (about 38 times), excellent work of extension (about 19 MJ m^?3), and full self‐recoverability (100% recovery of initial properties within 15 min at 50°C and within 60 min in ambient conditions, respectively). In addition, the hydrogels exhibited good self‐healing capabilities at ambient conditions (about 40% tensile strength recovery without any external stimuli). This work demonstrates that dual physical crosslinking combining hydrophobic interaction and ionic association can be achieved in single‐polymer hydrogels with significantly improved mechanical performance but without sacrificing favorable properties. POLYM. ENG. SCI., 59:145–154, 2019. © 2018 Society of Plastics Engineers     

Super‐Tough,Self‐Healing Polyurethane Based on Diels‐Alder Bonds and Dynamic Zinc–Ligand Interactions

Self‐healing polymer materials have attracted extensive attention and have been explored due to their ability of crack repairing in materials. This paper aims to develop a novel polyurethane‐based material with high self‐healing efficiency and excellent mechanical properties under 80 °C on the basis of reversible Diels–Alder bonds as well as zinc–ligand structure (DA‐ZN‐PU). By integrating DA bonds and zinc–ligand structure, as‐prepared DA‐ZN‐PU samples reach the maximum tensile strength as much as 28.45 MPa. After self‐healing, the tensile strength is 25.85 MPa, leading to the high self‐healing efficiency of 90.8%. In addition, by introducing carbonyl iron powder (CIP), a new polyurethane containing carbonyl iron powder (DA‐ZN‐CIP‐PU) can be achieved, exhibiting microwave‐assisted self‐healing property. And the self‐healing efficiency can be reached to 92.6% in 3 min. Due to high self‐healing efficiency and excellent mechanical properties of the prepared novel polyurethane, it has application attributes in crack repair of functional composite materials.     

A Novel Polyvinyl Alcohol-Based Hydrogel with Ultra-Fast Self-Healing Ability and Excellent Stretchability Based on Multi Dynamic Covalent Bond Cross-Linking

A novel self-healing poly(vinyl alcohol) (PVA)-based hydrogel is developed by cross-linking PVA chains through multi dynamic covalent bonds by use of a small cross-linker composed by 4-formylphenylboric acid (FPBA) and lysine (Lys). The dynamic borate-imine-imine-borate bond structure between PVA chains endows the hydrogel excellent stretchability and ultra-fast self-healing ability without external stimulation. The self-healing efficiency can attain 94% and the elongation at break can reach up to near 1000% after only 3 min healing. Moreover, the self-healing of the hydrogel through the contact of two faces from both the same cut position and different cut positions has similar excellent efficiency. The hydrogel with the unusual self-healing performance and stretchability is used as an ideal material in strain sensors monitoring human movement and tiny vibrations caused by human voice. Interestingly, the sensor can continue to function normally after self-healing for only ≈3 s. It is expected that this simple strategy of fabricating self-healing hydrogels with multi dynamic bonds will provide new opportunities in the design and preparation of PVA-based hydrogels to expand their potential applications in sensors and other various fields.     

Highly Flexible,Tough, and Self‐Healable Hydrogels Enabled by Dual Cross‐Linking of Triblock Copolymer Micelles and Ionic Interactions

Development of artificial soft materials that have good mechanical performances and autonomous healing ability is a longstanding pursuit but remains challenging. This work reports a kind of highly flexible, tough, and self‐healable poly(acrylic acid)/Fe(III) (PAA/Fe(III)) hydrogels. The hydrogels are dually cross‐linked by triblock copolymer micelles and ionic interaction between Fe(III) and carboxyl groups. Due to the coexistence of these two cross‐linking points, the resulting PAA/Fe(III) hydrogels are tough and can be flexibly stretched, bent, knotted, and twisted. The hydrogels can withstand a deformation of 600% and an ultimate stress as high as 250 kPa. Moreover, the dynamic ionic interaction also endows the hydrogels self‐healing properties. By varying the ratio of Fe(III)/AA, a compromised healing efficiency of 73% and an ultimate stress of 200 kPa are obtained.

     

Graphene Oxide Hybrid Supramolecular Hydrogels with Self‐Healable,Bioadhesive and Stimuli‐Responsive Properties and Drug Delivery Application

Self‐healable hydrogels are promising soft materials with great potential in biomedical applications due to their autonomous self‐repairing capability. Although many attempts are made to develop new hydrogels with good self‐healing performance, to integrate this characteristic along with other responsive multifunctions into one hydrogel still remains difficult. Here, a self‐healable hybrid supramolecular hydrogel (HSH) with tunable bioadhesive and stimuli‐responsive properties is reported. The strategy is imparting graphene oxide (GO) nanosheets and quadruple hydrogen bonding ureido‐pyrimidinone (UPy) moieties into a thermoresponsive poly(N‐isopropylacrylamide) (PNIPAM) polymer matrix. The obtained GO–HSH hydrogel shows rapid self‐healing behavior and good adhesion to various surfaces from synthetic materials to biological tissue. In addition, doxorubicin hydrochloride (DOX) release profiles reveal the dual thermo‐ and pH‐responsiveness of the GO–HSH hydrogel. The DOX‐loaded hydrogel can further directly adhere to titanium substrate, and the released DOX from this thin hydrogel coating remains biologically active and has high capability to kill tumor cells.     

Electrically conductive and mechanically tough graphene nanocomposite hydrogels with self‐oscillating performance

Conventional hydrogels are extremely brittle, fragile and poorly conductive, which limits their applications in a variety of aspects. In this study, we fabricated a novel kind of nanocomposite self‐oscillating hydrogel poly(AA‐co‐Fe(phen)₃)/PVA/RGO with high conductivity and good mechanical strength by dispersing reduced graphene oxide (RGO). Due to the synergetic effect of RGO dispersed in the hydrogels or dry gels and Fe metal which is the reduction product of the Fe(phen)₃ moiety by RGO, the hydrogels have a high conductivity of 18.2 S m^?1 with 0.67 wt% RGO content. The dispersed RGO in the hydrogels combined with the network structure by means of hydrogen bonding, π–π stacking and electrostatic interaction and was demonstrated to enhance the mechanical properties of the hydrogels. The elastic modulus achieves 65.2 kPa (1020% of the tensile strength) and 236.4 kPa (with 70% compression), respectively. In addition, the prepared hydrogels exhibit a self‐oscillating behavior in a Belousov–Zhabotinsky solution free of catalyst. These results can be broadly applied in the future in the development of an autonomous on–off switching, flexible/stretchable, graphene‐based soft electronic device. © 2019 Society of Chemical Industry     

Highly Mechanical and Fatigue‐Resistant Double Network Hydrogels by Dual Physically Hydrophobic Association and Ionic Crosslinking

Double network (DN) hydrogels with high strength and toughness are considered as promising soft materials. Herein, a dual physically cross‐linked hydrophobic association polyacrylamide (HPAAm)/alginate‐Ca²⁺ DN hydrogel is reported, consisting of a HPAAm network and a Ca²⁺ cross‐linked alginate network. The HPAAm/alginate‐Ca²⁺ DN hydrogel exhibits excellent mechanical properties with the fracture stress of 1.16 MPa (3.0 and 1.7 times higher than that of HPAAm hydrogel and HPAAm/alginate hydrogel, respectively), fracture strain of 2604%, elastic modulus of 71.79 kPa, and toughness of 14.20 MJ m^?3. HPAAm/alginate‐Ca²⁺ DN hydrogels also demonstrate self‐recovery, notch‐insensitivity, and fatigue resistance properties without any external stimuli at room temperature through reversible physical bonds consisting of hydrophobic association and ionic crosslinking. As a result, the dual physical crosslinking would offer an avenue to design DN hydrogels with desirable properties for broadening current applications of soft materials.     

High‐Strength,Rapidly Self‐Recoverable,and Antifatigue Nano‐SiO2/Poly(Acrylamide–Lauryl Methacrylate) Composite Hydrogels

Creating load‐bearing hydrogels with superior mechanical strength and toughness is of vital importance for promoting the development of polymer hydrogels toward practical applications. Herein, a type of composite hydrogel is facilely fabricated employing simple and effective UV irradiation one‐pot method by introducing cheap and available nanosilica sol into hydrophobic association poly(acrylamide–lauryl methacrylate) (HAPAM gels). Composite hydrogels exhibit enhanced mechanical strength (compression stress reaching 4.4 MPa) and toughness (compression hysteresis energy achieved is 151.15 kJ m^?3) compared to HAPAM gels. Composite hydrogels also demonstrate rapid self‐recovery behavior (95.91% stress recovery and 92.19% hysteresis energy recovery after restoration for 15 min, respectively) and favorable fatigue‐resistant ability without the help of external stimuli at room temperature based on the cyclic loading–unloading compression measurements. The simple and effective design strategy may help the development of hydrogel materials toward practical applications for soft sensors, tissue engineering, and actuators.     

An injectable and self‐healing novel chitosan hydrogel with low adamantane substitution degree

Chitosan (CS) is a semi‐natural polymer with supreme biological function, while the strong interchain hydrogen bonds cause poor water solubility and limit its broader use. To break the semi‐rigid structure of CS, a kind of CS modified by adamantane (AD‐CS) was successfully synthesized by amidation reaction with 1‐(3‐dimethylaminopropyl)‐3‐ethylcarbodiimide hydrochloride as catalyst. The chemical structure of AD‐CS was characterized by Fourier transform infrared spectroscopy and ¹H NMR. The AD substitution degree of CS is around 2%, calculated by ¹H NMR. A soft and transparent hydrogel composed of hydrogen bonds was obtained directly by simply adding a certain amount of water under mild conditions. Rheological measurements were carried out to research the mechanism of hydrogel formation by measuring the influence of different additives and conditions on the AD‐CS hydrogel. Reinforced hydrogels were prepared by freezing and thawing. The mechanical strength and self‐healing property of reinforced and pristine hydrogels were assessed with an oscillatory rheometer. The modulus of the reinforced hydrogel was obviously enhanced without much loss of self‐healing property. Other properties such as adhesion, injectability and temperature response were also studied. These injectable and self‐healing hydrogels show potential value in medical care. Additionally, this is a new method to design CS hydrogels with their original interchain hydrogen bonds. © 2019 Society of Chemical Industry