Self-healing quadruple shape memory hydrogels based on coordination,borate bonds and temperature with tunable mechanical properties

Quadruple shape memory hydrogels were prepared by one-pot in situ copolymerization using acrylamide, acrylic acid, agar, and poly(vinyl alcohol). The hydrogels have multiple reversible shape memory based on the coordination bonds of poly(acrylic acid) with Fe3+, borate bonds based on poly(vinyl alcohol), and hydrogen bonds of agar and poly(vinyl alcohol). The hydrogel demonstrated tunable mechanical properties when the hydrogels immersed in different solutions for various lengths of time. After immersion in the ferric chloride solution, tensile stress and elastic moduli of the hydrogels were enhanced with increasing soaking time. After immersion in the borax solution, tensile stress first increased and then decreased with increasing soaking time. Due to the reversible effect of the borate bond, the hydrogel achieved ultra-fast self-healing. The hydrogel after immersion in borax solution could begin healing in 24 h and healed at 44 h. The tensile stress and tensile strain of the self-healing hydrogel increased when soaking time increased from 48 to 96 h, and tensile stress at healing times of 96 h was nearly as the same as that of the original hydrogel when compared with it. The combination of tunable mechanical properties, efficient recoverability and self-healing abilities coupled with facile preparation endowed the developed hydrogel a high potential for use in biomedical applications.     

Dual-responsive shape memory hydrogels with self-healing and dual-responsive swelling behaviors

Shape memory hydrogels (SMHs) can fix the hydrogels in a provisional shape and restore the initial shape under external stimulation. Herein, a dual-responsive shape memory hydrogel with dual-responsive swelling and self-healing properties is presented in this work. The SMHs were fabricated by one-step emulsion copolymerization of acrylic acid (AAc), acrylamide (AAm) and stearyl methacrylate (SMA). Sodium alginate (SA) was introduced as an interpenetrating polymer in the network. With ionic cross-linking between -COO⁻ and Fe³⁺ or saline-reinforced hydrophobic association, the hydrogels can be fixed in a provisional shape, which can be restored by immersing the hydrogels in vitamin C solution or pure water, respectively. When the as-prepared hydrogels were immersed in FeCl₃ solutions, additional ionic cross-linking between Fe³⁺ and -COO⁻ could be formed, thus constructing the dual physically cross-linked (DPC) network, which endows the hydrogels with excellent fracture stress (2.6 MPa) and toughness (5.47 MJ/m³). Besides, the reversible physical cross-linkings endowed the hydrogel with outstanding self-healing capability. Furthermore, the pH and saline responsive swelling properties of the SMHs are additional fantastic properties. Therefore, we believe that this simple strategy provides a great opportunity for the preparation of SMHs with multiple intellectual performances.     

Multi-functional polyurethane composites with self-healing and shape memory properties enhanced by graphene oxide

Development of shape memory polymer materials with integrated self-healing ability, shape memory property, and outstanding mechanical properties is a challenge. Herein, isophorone diisocyanate, polytetramethylene ether glycol, dimethylglyoxime, and glycerol have been used to preparation polyurethane by reacting at 80°C for 6 h. Then, graphene oxide (GO) was added and the reaction keep at 80°C for 4 h to obtain polyurethane/GO composite with self-healing and shape memory properties. Scanning electron microscopy shows that the GO sheets were dispersed uniformly in the polyurethane matrix. The thermal stability was characterized by thermogravimetric analyses. The tensile test shows that the Young's modulus of the composites increases from 38.57 ± 4.35 MPa for pure polyurethane to 95.36 ± 10.35 MPa for the polyurethane composite with a GO content of 0.5 wt%, and the tensile strength increases from 6.28 ± 0.67 to 15.65 ± 1.54 MPa. The oxime carbamate bond and hydrogen bond endow the composite good self-healing property. The healing efficiency can reach 98.84%. In addition, the composite has excellent shape memory property, with a shape recovery ratio of 88.6% and a shape fixation ratio of 55.2%. This work provides a promising way to fabricate stimulus-responsive composite with versatile functions.     

Chitosan-based double network hydrogels with self-healing and dual-responsive shape memory abilities

Chitosan-based single network hydrogels with imine bonds have excellent self-healing capability, while poor mechanical properties limit their applications. Here, chitosan-polyacrylamide-based double network hydrogels were prepared via in situ free-radical polymerization of acrylamide in the presence of N-carboxyethyl chitosan (CEC) and dibenzaldehyde-terminated telechelic poly(ethylene glycol), which had excellent mechanical properties, self-healing, and dual-responsive shape memory abilities. The maximum tensile strength and elongation at break could reach 460 kPa and 4600%, respectively. Meanwhile, owing to the reversibility of imine bonds, elongation and strength at break of hydrogels could heal by 84.2 and 93.2% under alkali stimulation at 35 °C, respectively. Furthermore, the hydrogels also had good shape memory abilities for pH-stimuli responsiveness of the imine bonds and metal ions stimuli responsiveness of CEC. The prepared chitosan-based functional hydrogels have great potential application prospects in tissue scaffolds, actuators, and wearable devices. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48247.     

Glycerol-modified poly(vinyl alcohol)/poly(ethylene glycol) self-healing hydrogel for artificial cartilage

Poly(vinyl alcohol) (PVA) hydrogels have shown potential applications in bionic articular cartilage due to their tissue-like viscoelasticity, good biocompatibility and low friction. However, their lack of adequate mechanical properties is a key obstacle for PVA hydrogels to replace natural cartilage. In this study, poly(ethylene glycol) (PEG) and glycerol were introduced into PVA, and a PVA/PEG–glycerol composite hydrogel was synthesized using a mixing physical crosslinking method. The mechanical properties, hydrophilicity and tribological behavior of the PVA/PEG–glycerol hydrogel were investigated by changing the concentration of glycerol in PEG. The results showed that the tensile strength of the hydrogel reached 26.6 MPa at 270% elongation at break with 20 wt% of glycerol plasticizer, which satisfied the demand of natural cartilage. In addition, the excellent hydrophilicity of glycerol provides good lubricating properties for the composite gel under dry friction. Meanwhile, self-healing and cellular immunity assays demonstrated that the composite gel could have good self-healing ability and excellent biocompatibility even in the absence of external stimuli. This study provides a new candidate material for the design of articular cartilage, which has the potential to facilitate advances in artificial joint cartilage repair. © 2022 Society of Industrial Chemistry.     

Highly Stretchable,Strain-Sensitive,and Antifreezing Macromolecular Microsphere Composite Starch-Based Hydrogel

Starch-based hydrogel is widely used as an excellent biocompatibility and biodegradability material. However, due to the disadvantages of poor mechanical properties, brittleness, and low stretchability attribute that remains a challenge to prepare multifunctional starch hydrogel integrating high stretchability, strength, and conducting capacity. In this study, macromolecular microspheres with various wettability are successfully incorporated into the hydrogel prepared using the carboxymethyl starch and polyacrylamide cross-linked by Fe³⁺ and covalent cross-linker, respectively. The obtained double-network (DN) hydrogel performs good mechanical properties (the fracture stress 483 ± 38 kPa and the elongation at break 1615 ± 25%). Impressively, the obtained DN hydrogels by solvent soaking still maintain excellent mechanical strength and flexibility at −40 °C. Furthermore, it can be assembled to be a resistance-type strain sensor to detect multiscale strain. Therefore, the strategy can shed light on the preparation of multifunctional starch-based hydrogel for broad applications.     

A Dual Physical Cross-Linking Strategy to Construct Tough Hydrogels with High Strength,Excellent Fatigue Resistance,and Stretching-Induced Strengthening Effect

Hydrogels with excellent stiffness, toughness, anti-fatigue, and self-recovery properties are regarded as promising water-containing materials. In this work, a dual physically cross-linked (DPC) sodium alginate (SA)/poly[acrylamide (AAm)-acrylic acid (AAc)-octadecyl methacrylate (OMA)]-Fe³⁺ hydrogel is reported, which is constructed by hydrophobic association (HA) and ionic coordination (IC). The optimal DPC hydrogel demonstrates excellent mechanical performance: tensile modulus of 0.65 MPa, tensile strength of 3.31 MPa, elongation at break of 1547%, and toughness of 27.8 MJ m^–3. SA/P(AAm-AAc-OMA)-Fe³⁺ DPC hydrogels also exhibit prominent anti-fatigue and self-recovery performance (99.1–109.7% modulus recovery and 90.4–108.9% dissipated energy recovery after resting for 5 min without additional stimuli at ambient temperature) through the reconstruction of reversible physical cross-linking. Some of the SA/P(AAm-AAc-OMA)-Fe³⁺ DPC hydrogels even exhibit a stretching-induced strengthening effect, which is similar to the performance of muscle—“the more training, the more strength.” Hence, the combination of HA and IC will provide an effective approach to design DPC hydrogels with desirable mechanical performances and a longer service life for wider applications of soft materials.     

Development of a Strong,Recyclable Poly(dimethylsiloxane) Elastomer with Autonomic Self-Healing Capabilities and Fluorescence Response Properties at Room Temperature

With the recent emphasis on environmental protection measures, there are increasingly strong demands for environment-friendly multifunctional materials, so research regarding high-performance, recyclable, functional materials with self-healing abilities is of great interest. However, the comprehensive mechanical properties of most available self-healing materials are insufficient; to date, most developed materials are either tough but brittle or flexible but weak. This report describes the application of a crosslinking strategy based on multiple dynamic bonds for the development of an autonomically self-healing, multifunctional, boroxine-containing poly(dimethylsiloxane) elastomer (PDMS-BN). This approach takes advantage of well-designed intermolecular and intramolecular nitrogen-coordinated boroxines by using a synergetic dynamic mechanism. The elastomers exhibit enhanced comprehensive mechanical properties (with maximum strength up to 1.72 MPa, elongation at break up to 307%, Young's modulus up to 11.18 ± 0.52 MPa, and toughness up to 4.92 MJ m⁻³) and highly autonomic self-healing capabilities, with ≈96% efficiency at room temperature for 48 h. Moreover, the PDMS-BN elastomer can be recycled multiple times via crushing/molding or disassembling/casting processes, without losing their original mechanical robustness. The as-prepared elastomers also demonstrate good adhesive properties and a unique fluorescence-quenching response in the presence of Fe³⁺ ions.     

A Dual‐Crosslinked Strategy to Construct Physical Hydrogels with High Strength,Toughness, Good Mechanical Recoverability,and Shape‐Memory Ability

A novel type of physical hydrogel based on dual‐crosslinked strategy is successfully synthesized by micellar copolymerization of stearyl methacrylate, acrylamide, and acrylic acid, and subsequent introduction of Fe³⁺. Strong hydrophobic associations among poly(stearyl methacrylate) blocks form the first crosslinking point and ionic coordination bonds between carboxyl groups and Fe³⁺ serve as the second crosslinking point. The mechanical properties of the hydrogel can be tuned in a wide range by controlling the densities of two crosslinks. The optimal hydrogel shows excellent mechanical properties (tensile strength of ≈6.8 MPa, elastic modulus of ≈8.0 MPa, elongation of ≈1000%, toughness of 53 MJ m^?3) and good self‐recovery property. Furthermore, owing to stimuli responsiveness of physical interaction, this hydrogel also shows a triple shape memory effect. The combination of two different physical interactions in a single network provides a general strategy for designing of high‐strength hydrogels with functionalities.     

A Biomimetic Hybrid Hydrogel Based on the Interactions between Amino Hydroxyapatite and Gelatin/Gellan Gum

In this work, a gelatin (Gel)‐oxidized gellan gum (OG)/amino hydroxyapatite (mHap) hybrid hydrogel with Schiff base linkages is reported. The mHap is obtained by modifying hydroxyapatite with tetraethyl orthosilicate and 3‐aminopropyl‐triethoxysilane. The effects of different mHap contents on the structure, morphology, and properties of hydrogels are particularly investigated. Scanning electron microscopy coupled with energy dispersion spectroscopy reveals that mHap of around 100 nm is uniformly distributed inside the hydrogel with interconnected porous structures. Notably, the hydrogel with 1 wt% mHap possesses the highest compressive stress (2.01 ± 0.10 MPa) at 90% strain, as well as the lowest equilibrium swelling ratio (97% ± 5%) and degradation rate than other hydrogels. Besides, an ultra‐high compressive stress equivalent to 91% of the initial stress can be obtained by this hydrogel after 50 loading‐unloading cycles (85% strain). Meanwhile, after being swollen, this improved hydrogel also exhibits better structural stability than Gel‐OG hydrogel. The in vitro 3‐(4,5‐dimethylthiazol‐2‐yl)‐2,5‐diphenyltetrazolium bromide (MTT) assay further shows that all hydrogels are nontoxic against mouse fibroblasts. This work provides a biomimetic strategy to construct the organic/inorganic hydrogels with excellent interactions, elasticity, reversibility, and biocompatibility, which is of great importance for the practical applications in cartilage tissue engineering.     

Quickly self-healing hydrogel at room temperature with high conductivity synthesized through simple free radical polymerization

The use of conductive self-healing hydrogels in electronic devices not only reduces replacement and maintenance costs but also prolongs their lifetime. Therefore, developing hydrogels with autonomous self-healing properties and electronic conductivity is vital for the advancement of emerging fields, such as conductors, semiconductors, sensors, artificial skin, and electrodes and solar cells. However, it remains a challenge to fabricate a hydrogel with high conductivity that can be healed quickly at room temperature without any external stimulus. In this work, we report an effective and simple free radical polymerization approach to synthesizing a hydrogel using modified rGO and acrylate monomers containing abundant ion groups. The hydrogel exhibits excellent electronic conductivity, extremely fast electronic self-healing ability, and excellent repeatable restoration performance at 25 °C. The conductivity of the hydrogel reaches 27.2 S/m, the hydrogel recovers its original shape, and scoring scratched on the surface totally disappears after holding at 25 °C for 40 s. This conductive, room-temperature self-healing hydrogel takes unique advantage of supramolecular chemistry and polymer nanoscience and has potential applications in various fields such as self-healing electronics, artificial skin, soft robotics, biomimetic prostheses, and energy storage. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47379.     

Dual Cross-Linked Polymethacrylic Acid Hydrogels with Tunable Mechanical Properties and Shape Memory Behavior

Herein, a series of poly(methacrylic acid) hydrogels are prepared via bulk polymerization of methacrylic acid (MAAc) and grafting of Triton X-100 (TX-100). One-pot and extremely simple chemistry consist of only mixing and subsequently heating of commercially available monomer and surfactant. The polymer chains are interconnected through dual physical cross-link points formed by the hydrophobic associations in the center of TX-100 micelles and hydrogen bonds stabilized by hydrophobic α-methyl groups of MAAc. The hydrogels exhibit tunable mechanical properties ranging between softness and stiffness by adjusting the surfactant/monomer molar ratio, such as Young modulus of 0.6−22 MPa, elongation at break of 750−1700%, tensile strength of 0.21−3.6 MPa, and compressive strength of 41−93 MPa. The synergistic effect of high-density hydrogen bonds with hydrophobic associations endows a plastic-like hydrogel with high strength and shape memory (SM) behavior, while a high concentration of micelles with low-density hydrogen bonds endows a stretchable elastic hydrogel. The combination of temperature-induced SM property and wide-ranging mechanical performance will make such hydrogels useful in diverse applications.     

Synthesis of dual physical self-healing starch-based hydrogels for repairing tissue defects

Hydrogels have the potential to simulate and permeate body tissues. They can be used in many biomedical applications, such as drug delivery, wound dressings, contact lenses, synthetic implants, biosensors, and tissue engineering. Despite recent significant advances in hydrogel fabrication, with the introduction of double network hydrogels, with ionic or hydrogen bonds, there is still the challenge of achieving optimal mechanical properties with appropriate self-healing ability. To solve the above problem, in this study, a new type of starch/chitosan/PVA/borax hydrogel was synthesized by adopting the one-pot method. The effect of concentration and ratio of raw materials on the final properties of hydrogels, such as the degree of hydrophilicity, morphology, degradation, mechanical strength, and drug release rate, was investigated. The properties of hydrogels were examined by scanning electron microscopy, thermogravimetric analysis, Fourier-transform infrared spectroscopy, X-ray diffractometry, and contact angle, which confirmed the composite synthesis and uniform distribution of HNT and curcumin. In addition, the composite hydrogel showed excellent mechanical properties. Drug release studies confirmed that the drug is slowly released from the nanocomposite hydrogels. The results showed that starch-based nanocomposite hydrogels could provide appropriate repairing potential for defects exposed to changeable parameters.     

Self-healable polyacrylic acid-polyacrylamide-ferric ion dual-crosslinked hydrogel with good biotribological performance as a load-bearing surface

Although having been widely investigated, polymer hydrogels still have many defects like poor tribological properties and insufficient durability, hindering their further applications in biomedical fields. In this study, we present a simple method to synthesize polyacrylic acid-polyacrylamide-ferric ion (PAA-PAAm-Fe³⁺) dual-crosslinked hydrogels with self-healing abilities and “soft-hard” hydrogel-polyetheretherketone (PEEK) combined load-bearing surfaces with low friction coefficients. After analytical characterizations, the results demonstrated that the hydrogels could repair themselves without any external stimuli. Because of the excellent biphasic and aqueous lubrication provided by the hydrogel layer and the load-bearing capacity provided by the PEEK substrate, the friction coefficient of a load-bearing surface was as low as 0.048 in water, much lower than a pristine PEEK block or a hydrogel block sample. This work fabricated self-healable PAA-PAAm-Fe³⁺ hydrogels and low friction bearing surfaces, successfully improving the tribology properties of hydrogels, hopefully promoting their applications as biomedical materials such as articular cartilage. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48499.     

Reinforcing biopolymer hydrogels with ionic‐covalent entanglement hydrogel microspheres

Microscopic hydrogel spheres can be used to improve the mechanical properties of conventional hydrogels. We prepared ionic‐covalent entanglement (ICE) hydrogel microspheres of calcium cross‐linked gellan gum and genipin cross‐linked gelatin using a water‐in‐oil emulsion‐based processing technique. The method was optimized to produce microspheres with number average diameter 4 ± 1 µm. These ICE microspheres were used to reinforce gelatin hydrogels and improve their compressive mechanical properties. The strongest microsphere reinforced hydrogels possessed a compressive mechanical stress at failure of 0.50 ± 0.1 MPa and a compressive secant modulus of 0.18 ± 0.02 MPa. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40557.     

Facile fabrication of tough and biocompatible hydrogels from polyvinyl alcohol and agarose

A polyvinyl alcohol (PVA)-agarose (agar) composite hydrogel (M-PVA-agar-60) was developed by simple three cycles of freeze-thawing, followed by successively soaking in ammonium sulfate aqueous solution to induce phase separation and dialyzing against deionized water to remove residual sulfate salts. Due to the synergy of crystalline regions, hydrogen bonding and phase separation domains, the obtained M-PVA-agar-60 hydrogel exhibits excellent mechanical properties (tensile strength = 1.1 MPa, tensile strain = 324% and compressive stress = 12.5 MPa), combined with a high water content of 87.0%. Moreover, the hydrogel hardly expands after immersing in the phosphate-buffered saline aqueous solution at 37°C for a week, and the tensile stress and toughness remain almost the same as their initial values, superior to most reported non-swellable hydrogels. Because of the biocompatible starting materials, absence of toxic chemicals, and dialysis in advance to remove ammonium sulfate, the hydrogel also shows excellent cell compatibility, making it an ideal candidate for tissue engineering materials.     

Intelligent self-healable electroactive carboxymethyl cellulose hydrogel containing conductive polythiophene and acid hydrolyzed cellulose

Self-healable electroactive carboxymethyl cellulose/polythiophene/acid hydrolyzed cellulose (CMC/PTh/AHC) hydrogels were successfully fabricated. AHC particles dispersed well in the CMC matrix improving hydrogels thermal stability. The electro-responsive performance of the hydrogels was investigated with respect to bending angle and bending sensitivity. The results showed that under an applied electric field, the CMC/PTh/AHC hydrogels bend toward a cathode electrode. In addition, the electroactive performance of the hydrogels decreased with increased AHC content. The CMC/PTh/AHC10 (10 wt.% AHC) hydrogel exhibited the shortest induction time (τ_ind) of 3.35 ± 0.56 s. For self-healing, it was found that the hydrogel with addition of 2 wt.% AHC had the highest self-healing efficiency on both tensile strength and elongation at break (93.37 ± 3.17% and 99.35 ± 12.11%, respectively). While the self-healing efficiency on bending angle was 82.73 ± 14.55%. The results demonstrated that the properties of the CMC/PTh/AHC2 hydrogel were close to its original properties after healing for 24 h. The results demonstrated that the CMC/PTh/AHC hydrogel can be utilized as an actuator or artificial muscle using electrical stimulus.     

Thermoresponsive nanocomposite hydrogels with high mechanical strength and toughness based on a dual crosslinking strategy

The practical application of thermoresponsive poly(N-isopropylacrylamide) (PNIPAM) hydrogels are severely limited by their poor mechanical properties. Herein, we reported a series of dual crosslinked (DC) PNIPAM hydrogels with superior mechanical properties prepared by simple copolymerization of N-isopropylacrylamide and sodium acrylate (SA) in the laponite RDS suspension, following by a soaking process in multivalent metal cations (e.g., Ca²⁺, Al³⁺, Fe³⁺) aqueous solutions to form ionic coordination interactions with  COO groups of copolymer side chains. The effect of laponite RDS, AANa (sodium acrylate), and metal cation (e.g., Fe³⁺) concentrations on the mechanical properties and deswelling properties of the DC hydrogels are evaluated. The DC hydrogel prepared with 10 w/v% laponite RDS, 0.25 mol/L AANa and 0.45 mol/L Fe³⁺ possesses the best mechanical properties (ca. 1.1 MPa of tensile strength, 9.1 MPa of compression strength at 80% of compression strain, 1.4 MPa of elastic modulus and 1.3 MJ/m³ of toughness). Moreover, we also discovered that the DC hydrogels crosslinked by Fe³⁺ showed better mechanical properties due to the larger charge and ion radius of Fe³⁺.     

Facile fabrication method of hydrophobic-associating cross-linking hydrogel with outstanding mechanical performance and self-healing property in the absence of surfactants

A cationic surfactant monomer, dimethyldodecyl(2-acrylamidoethyl)ammonium bromide (AMQC₁₂) was synthesized. A family of hydrophobic-associating cross-linking hydrogels (HAC-gels) fabricated via the self-assembly of amphiphilic multiblock copolymers of acrylamide and AMQC₁₂ can be synthesized by free-radical aqueous solution micelle copolymerization in the absence of surfactants using the one-pot method. The HAC-gels possessed outstanding mechanical performance, with optimal tensile strength, compressive strength, and elongation at break of 250 kPa, 14 MPa, and 1850%, respectively. Meanwhile, the HAC-gels exhibited self-healing property, and tetrahydrofuran (THF) significantly accelerated their self-healing process. The recovery hysteresis of hydrophobic-associating hydrogels prepared in the presence of surfactants can be eliminated because of homogeneity of the hydrogel network and the dynamic and mobile properties of physical cross-linking junctions. Investigations on the mechanical property and structure evolution of hydrogels revealed that the hydrophobic-associating interaction was the driving force of self-assembly of amphiphilic multiblock copolymers. Furthermore, spherical micelles and macroscopic cross-linking network can be easily switched reversibly by regulating copolymers concentration.     

Self-assembly and metal ions-assisted one step fabrication of recoverable gelatin hydrogel with high mechanical strength

ABSTRACT

Gelatin hydrogel has been widely applied in bio-applications due to their good biocompatibility and high water content. However, poor mechanical properties of gelatin hydrogel greatly limit their application. Here we present a facile one-step soaking method to fabricate a recoverable gelatin hydrogel with high mechanical property, which is based on hydrogen bonds and metal ionic interaction. The mechanical properties of gelatin hydrogels can be tuned with different metal ions, temperatures and soaking times. Especially, gelatin-Fe³⁺ hydrogel can reach to 65 MPa compression stress with the compressive strain over 99% and possess good fatigue resistance under cyclic loadings. Besides, hydrogels crosslinked with metal ions show better antibacterial ability against Escherichia coli and Staphylococcus aureus. This work suggested an alternative for the design of tough gelatin-based hydrogels with desirable properties, which may hold promising for potential bio-applications under physiological conditions.