Fabrication of tough,self-recoverable,and electrically conductive hydrogels by in situ reduction of poly(acrylic acid) grafted graphene oxide in polyacrylamide hydrogel matrix

Developing electrically conductive hydrogels with good electronic properties and excellent mechanical performance is significant to their potential applications. In this article, we present a strategy to fabricate tough, self-recoverable and electrically conductive hydrogels containing reduced graphene oxide (rGO). Poly(acrylic acid) grafted graphene oxide (GO-g-PAA) was synthesized and incorporated into chemically crosslinked polyacrylamide (PAM) networks to obtain GO-g-PAA/PAM hydrogels, which were further treated with ascorbic acid solution at ambient temperature to give rGO-g-PAA/PAM hydrogels. The interfacial interaction between GO/rGO and hydrogel matrix was improved by reversible hydrogen bonds between the grafted PAA chains and PAM matrix. Consequently, both GO-g-PAA/PAM and rGO-g-PAA/PAM hydrogels exhibited improved tensile properties, excellent energy dissipation, and rapid self-recovery. The in situ chemical reduction of GO-g-PAA in hydrogel matrix endowed rGO-g-PAA/PAM hydrogels with satisfactory electrical conductivity and obvious resistance change upon stretching. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48781.     

Janus POSS-based hydrogel electrolytes with highly stretchable and low-temperature resistant performances for all-in-one supercapacitors

Conductive hydrogels can be utilized in the field of flexible supercapacitors due to their stretchable properties and high ionic conductivity. However, many of the conductive hydrogels lose their stretchability and conductivity at subzero temperatures. Herein, a novel Janus POSS-based hydrogel electrolyte that shows excellent flexibility and ionic conductivity at low temperatures is designed and prepared by the copolymerization of acrylamide and a water-soluble Janus-type polyhedral oligomeric silsesquioxane (AS-POSS) containing sodium sulfonate groups and double bonding groups. The sodium sulfonate groups of AS-POSS and LiCl endow the hydrogel electrolyte with excellent anti-freezing ability. Simultaneously, the double bonding groups of AS-POSS enable a successful POSS crosslinking in the polymer network, resulting in a highly stretchable hydrogel electrolyte (1445%) with high ionic conductivity (0.067 S cm⁻¹) at −20°C. Thereafter, the all-in-one flexible supercapacitor is prepared by in-situ polymerization of aniline. Based on the exceptional anti-freezing properties of the Janus POSS-based hydrogel electrolyte, the all-in-one supercapacitor exhibits stable electrochemical performance (>90% capacitance retained under deformation at −20°C) and excellent cycling stability (only 19.7% capacitance decay over 2000 charge/discharge cycles at −20°C) at low temperatures. The Janus POSS-based hydrogel electrolyte is expected to be a promising gel electrolyte for an all-in-one supercapacitor that resists freezing.     

Production of reduced graphene oxide-based electrically conductive hydrogel by using modified chitosan

Herein, a new approach was applied to produce reduced graphene oxide (RGO)-based conductive hydrogel by using modified chitosan (CTS) as a primary constituent. A variety amounts of RGO (from 0 to 15%) were incorporated into the polymeric network generated by photopolymerization of CTS-graft-glycidyl methacrylate (CTS-g-GMA) and poly(ethylene glycol)diacrylate (PEGDA). The structures of hydrogels were confirmed by FT-IR, XRD, and SEM analyses. Water uptake capacity of hydrogels determined gravimetrically. L929 fibroblast cells were used for cytotoxicity test. According to conductivity measurements carried out by four-point probe technique, the highest conductivity (1.716 × 10⁻³ S/cm) was obtained when 10% RGO was encapsulated into the polymeric structure. From the results, it could be envisaged that electroconductive hydrogel (ECH) fabricated in this study could have a potential usage for biosensor applications in the future projects. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48008.     

Self-healing and conductivity of chitosan-based hydrogels formed by the migration of ferric ions

The currently reported self-healing hydrogels have problems of low mechanical strength, single performance, and poor self-healing efficiency, which greatly limit their applications. Here, through adding N-carboxyethyl chitosan to acrylic-Fe³⁺ system, the self-healing physically crosslinked hydrogels were prepared via in situ free radical polymerization, which have excellent self-healing ability and mechanical properties. The maximum tensile strength and elongation at break of the hydrogels can reach up to 280 KPa and 1900%, respectively. Owing to the reversibility of coordination, self-healing efficiency of the hydrogels can reach 98% in 2.5 h. Moreover, the hydrogels also have good conductivity due to the migration of Fe³⁺. This strategy can broaden the applications of chitosan-based self-healing hydrogels. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47885.     

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.     

导电水凝胶的制备及应用研究进展

导电水凝胶是一类将亲水性基质和导电介质有机结合的新型水凝胶,具有较高的柔韧性、可调的力学性能和优异的电化学性能,在柔性电子设备等领域具有广阔的应用前景。本文综述了导电水凝胶材料的研究前沿和动态,介绍了导电水凝胶的分类及制备方法,讨论了导电水凝胶的结构设计与性能,重点阐述了导电水凝胶材料的应用研究进展,归纳了导电水凝胶材料面临的问题与挑战,并展望了导电水凝胶材料的发展趋势,指出采用天然可再生资源为原料开发具有高导电性、力学性能稳定、耐极端温度、生物相容性和生物可降解的导电水凝胶将成为下一步研究重点,同时优化柔性电子装置、提高器件输出稳定性也将成为重要的研究方向之一。导电水凝胶的制备及应用研究将促进柔性电子功能材料领域的快速发展。     

Boron Nitride Nanosheets Strengthened PVA/Borax Hydrogels with Highly Efficient Self-Healing and Rapid pH-Driven Shape Memory Effect

Self-healing hydrogels often possess poor mechanical properties which largely limits their applications in many fields. In this work, boron nitride nanosheets are introduced into a network of the poly(vinyl alcohol)/borax (PVA/borax) hydrogels to enhance the mechanical properties of the hydrogel without compromising the self-healing abilities. The obtained hydrogels exhibit excellent mechanical properties with a tensile strength of 0.410 ± 0.007 MPa, an elongation at break of 1712%, a Young's Modulus of 0.860 ± 0.023 MPa, and a toughness of 3.860 ± 0.075 MJ m⁻³. In addition, the self-healing efficiency of the hydrogels is higher than 90% within 10 min at room temperature. Benefiting from the excellent self-healing properties, the shapeability of the hydrogel fragments is observed using different molds. In addition, the hydrogels display rapid pH-driven shape memory effects and can recover to their original shape within 260 s. Overall, this work provides a new approach to hydrogels with integrated excellent mechanical properties, self-healing abilities, and rapid pH-driven shape memory effects.     

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.     

One-step preparation of poly(NIPAM-pyrrole) electroconductive composite hydrogel and its dielectric properties

Conductive polymers and hydrogels are two of the hot prospect polymer types that are used for new stimuli responsive materials. In this study, one-step preparation of electroconductive composite hydrogels containing polypyrrole (PPy) and N-isopropylacrylamide (NIPAM) using free radical polymerization technique was achieved with N,N-methylenebisacrylamide as a crosslinker and ammonium peroxy disulphate (APS) as initiator, in mixture of water/isopropyl alcohol. The equilibrium swelling degree of the poly(NIPAM)-pyrrole) electroconductive composite hydrogel was 9.88 g of H₂O/g dry polymer. According to TGA results, the thermal stability of the prepared composite poly(NIPAM-PPy) conductive hydrogel (700°C) hydrogel is higher than that of pure poly(NIPAM) hydrogel (600°C). Furthermore, prepared samples were characterized by FTIR, and SEM analyzes. Later, the samples were pressured into pellets so that electrical impedance spectroscopy (EIS) measurements were taken between 10 and 10 MHz at room temperature. The dielectric constant value of composite poly(NIPAM-PPy) hydrogel at 10 Hz is almost 10 times higher than that of poly(NIPAM) hydrogel. Both samples' real and imaginary parts of dielectric constant decreased with increased frequency. Samples exhibited non-Debye relaxation since experimental data fit into dielectric model of Havriliak-Negami. Moreover, low frequency data yielded d.c. conductivity of the pure and composite samples as 3.74 × 10⁻¹¹ and 1.02 × 10⁻⁸ S/cm, respectively. Real part of impedance at low frequencies also points out ~10³ times lower resistance values at 10 Hz for composite poly(NIPAM-PPy) hydrogel. Therefore, EIS results support that electroconductive composite hydrogel fabrication was achieved using free radical polymerization technique.     

Irreversible and Self-Healing Electrically Conductive Hydrogels Made of Bio-Based Polymers

Electrically conductive materials that are fabricated based on natural polymers have seen significant interest in numerous applications, especially when advanced properties such as self-healing are introduced. In this article review, the hydrogels that are based on natural polymers containing electrically conductive medium were covered, while both irreversible and reversible cross-links are presented. Among the conductive media, a special focus was put on conductive polymers, such as polyaniline, polypyrrole, polyacetylene, and polythiophenes, which can be potentially synthesized from renewable resources. Preparation methods of the conductive irreversible hydrogels that are based on these conductive polymers were reported observing their electrical conductivity values by Siemens per centimeter (S/cm). Additionally, the self-healing systems that were already applied or applicable in electrically conductive hydrogels that are based on natural polymers were presented and classified based on non-covalent or covalent cross-links. The real-time healing, mechanical stability, and electrically conductive values were highlighted.     

Effects of oxidant and dopants on the properties of cellulose/PPy conductive composite hydrogels

Cellulose/Polypyrrole (PPy) composite hydrogels were prepared by in situ chemically oxidative polymerization of pyrrole in the cellulose matrix. Ferric chloride (FeCl₃) was used as an oxidant and four sulfonic compounds were used as dopants in order to investigate the effects on the properties of cellulose/PPy conductive composite hydrogels. The extent of polymerization of PPy was determined by the amount of the oxidant and the composite hydrogels with oxidant at 0.3M?0.5M exhibited the higher conductivities for the intrachain and interchain conductivities of conductive polymers; the fracture stress of the composite hydrogels could be up to 26.25 MPa with a strain of 86.8% when the oxidant was at 0.5M. Doping is an efficient way to improve the conductivity of the composite hydrogels and four kinds of dopant were compared in this work. Long alkane chain and side group in dopants can increase the steric hindrance of PPy polymerization which resulted in the lower conductivity of the composite hydrogels compared to dopants with smaller steric hindrance. The conductivity of the composite hydrogel firstly increased and then decreased with the concentration of dopants from 0.1M to 1.0M in this work. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43759.     

Preparation and property of starch nanoparticles reinforced aldehyde–hydrazide covalently crosslinked PNIPAM hydrogels

Injectable, de‐crosslinkable, and thermosensitive hydrogels are obtained by hydrazide‐functionalized poly(N‐isopropylacrylamide) and aldehyde‐functionalized dextrin through in situ crosslinked method. Natural based and degradable starch nanoparticles (SNPs) are used as fillers in order to improve mechanical property of hydrogels. Internal morphology, dynamic modulus, thermosensitivity property, de‐crosslinking performance, drug release, and in vitro cytotoxicity of hydrogels are investigated. Results show that SNPs disperse well throughout hydrogel and have no significant influence on gelation time and de‐crosslinking performance. Elasticity property of composite hydrogel prepared from 9.0 wt % precursors with 1.5 wt % fillers is improved significantly by SNPs and maximum storage modulus reaches 399.2 kPa, but 89.6 kPa of unreinforced hydrogels. Hydrogels exhibit good thermosensitive performance at alternating cyclic temperature of 25 and 37 °C. Doxorubicin hydrochloride‐loaded hydrogels can release more than 25 days. No significant cytotoxicity to L929 fibroblast cells is observed through a CCK‐8 assay for hydrogels, precursors, and SNPs. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45761.     

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.     

Recent advances in shear-thinning and self-healing hydrogels for biomedical applications

Shear-thinning and self-healing hydrogels are being investigated in various biomedical applications including drug delivery, tissue engineering, and 3D bioprinting. Such hydrogels are formed through dynamic and reversible interactions between polymers or polypeptides that allow these shear-thinning and self-healing properties, including physical associations (e.g., hydrogen bonds, guest–host interactions, biorecognition motifs, hydrophobicity, electrostatics, and metal–ligand coordination) and dynamic covalent chemistry (e.g., Schiff base, oxime chemistry, disulfide bonds, and reversible Diels–Alder). Their shear-thinning properties allow for injectability, as the hydrogel exhibits viscous flow under shear, and their self-healing nature allows for stabilization when shear is removed. Hydrogels can be formulated as uniform polymer and polypeptide assemblies, as hydrogel nanocomposites, or in granular hydrogel form. This review focuses on recent advances in shear-thinning and self-healing hydrogels that are promising for biomedical applications. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48668.     

A highly elastic and sensitive sensor based on GSP/HPAM composited hydrogel

Development of conductive hydrogels to mimic the structures and properties of human skin has attracted enormous scientific interests. However, applications of such materials are often restricted by their poor mechanics and moderate sensitivities. Herein, a highly-stretchable, self-healing, and conductive hydrogel, comprised of grape seed extracted polymer and hydrophobically associated polyacrylamide (GSP-HPAM), was fabricated by simple mixing and in-situ polymerization. Compared with the single HPAM gels, the rigid GSP polymer could form sufficient hydrogen bonds and ionic interactions, which endowed the gel with effective energy dissipation mechanism and greatly improved the uniformity of network. As a result, the GSP-HPAM gel exhibited enhanced mechanics, that is, the tensile strength, strain, and compression stress of GSP-HPAM hydrogel were 0.7 MPa, 3000% and 28.3 MPa, respectively. Furthermore, the gel demonstrated linear strain-dependant conductivity between 0% and 1000% with gauge factor around 3.43, superior to most hydrogel-based strain sensors. In addition, the gel was able to monitor human body motion, such as, finger bending and pulse rate. This multiple functional gel might find potential applications in artificial skin, soft robotics, and wearable devices.     

MWCNTs reinforced conductive,self-healing polyvinyl alcohol/carboxymethyl chitosan/oxidized sodium alginate hydrogel as the strain sensor

The preparation and application of hydrogel has been a hot research field in recent years. Here in, a composite hydrogel based on poly(vinyl alcohol) (PVA), carboxymethyl chitosan (CMCS), oxidized sodium alginate (OSA), and oxidized multiwall carbon nanotubes (OMWCNTs) was successfully prepared. Hydrogen and imine bonds of the hydrogel endowed the composite hydrogel with self-healing property and pH sensitivity. The fracture strength of the hydrogel was enhanced to about 0.8 MPa with the help of OMWCNTs, which was about 2.5 times compared with the one without OMWCNTs. Meanwhile, a new conductive network inside the hydrogel was constructed by OMWCNTs, which improved the conductivity of the hydrogel from 1.75 × 10⁻⁴ to 7.02 × 10⁻⁴ S/cm. The sensing test of the hydrogel showed that it could produce profound feedback signals for the deformation caused by external force and response to human body movements, such as finger bending, swallowing, and speaking.     

Investigation of the properties of conductive hydrogel composite containing Zn particles

In this work, the conductive hydrogel composites containing Zn particle synthesized and their electrical and thermal properties were investigated. Polyacrylamide/Zn composites were synthesized by free radical polymerization in aqueous solution. The effect of preparation conditions such as the influence of crosslinker amount, initiator amount, Zn amount, and water absorbency on electrical conductivity of hydrogel was investigated. The effect of preparation conditions on thermal properties has been characterized using thermogravimetric analysis (TGA) method. The structures of metal‐composites were evaluated by FTIR and scanning electron microscopy (SEM) methods. SEM revealed a more uniform pore size when Zn particles were used when compared with pure polyacrylamide. TGA curves showed that both hydrogels were stable upto 600°C. The Zn/polyacrylamide hydrogels have a good conductivity of 4.30 mS cm^?1. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Thermosensitive poly(n‐isopropylacrylamide) hydrogels bonded on cellulose supports

A two‐step initiation and polymerization process was developed for the preparation of two series of hydrogel–cellulose composites with distinctively different morphologies and swelling behaviors. Hydroentangled cotton cellulose fibers were optimally initiated in 20 mM aqueous ammonium cerium(IV) nitrate for 15 min and then polymerized in aqueous solutions of N‐isopropylacrylamide (NIPAAm) monomer and N,N′‐methylene bisacrylamide (BisA) crosslinker. The extents of hydrogels on the cellulose solids could be controlled by variations in the concentrations of the monomer and crosslinker as well as the NIPAAm/BisA solution‐to‐solid ratios. The two series of hydrogel–cellulose composites formed were hydrogel‐covered/filled cellulose (I) and cellulose‐reinforced hydrogel (II) composites. Series I composites were synthesized with NIPAAm/BisA solutions below the liquid saturation level of the cellulose; this led to pore structures (size and porosity) that depended on both the extent and swelling of the grafted hydrogels. Series II composites were polymerized in the presence of excessive NIPAAm/BisA solutions to produce cellulose solids completely encapsulated in the hydrogels. All the cellulose‐supported hydrogels exhibited lower extents of phase transition over a wider temperature range (28–40°C) than the free poly(N‐isopropylacrylamide) hydrogels (32°C). These findings demonstrate that hydrogels can be used to control the pore structure of cellulose and can be supported with cellulose fibers. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 999–1006, 2003     

Superfast Self‐Healing and Photothermal Active Hydrogel with Nondefective Graphene as Effective Additive

2D graphene with high quality holds great promise in improving the performance of the hydrogels owing to its exceptional electronic, thermal, and mechanical properties. However, the structure defects existed in graphene restrict its further applications. Herein, a simple and green method of fabricating defect‐free graphene nanosheets with the assistance of supercritical carbon dioxide (SC CO₂) is designed. The graphene nanosheets directly assemble with acrylic acid monomer and clay, and a flexible semitransparent hydrogel is fabricated. Benefiting from the excellent properties of the defect‐free graphene, the hydrogel exhibits the high mechanical performance, superfast self‐healing capability, excellent conductivity, and super photothermal conversion efficiency. According to the advantages above, the graphene/poly(acrylic acid)/clay hydrogels can be used for intelligent sensors for disease diagnosis, artificial electronic skin, and military stealth materials in the near future.     

Synthesis and characterization of poly{N‐[3‐(dimethylamino) propyl] methacrylamide‐co‐itaconic acid} hydrogels for drug delivery

A novel pH‐sensitive hydrogel system composed of itaconic acid (IA) and N‐[3‐(dimethylamino) propyl] methacrylamide was designed. This system was prepared by aqueous copolymerization with N,N‐methylene bisacrylamide as a chemical crosslinker. The chemical structure of the hydrogels was characterized by Fourier transform infrared (FTIR) spectroscopy. The microstructure and morphology of the hydrogels were evaluated by X‐ray diffraction (XRD) and scanning electron microscopy (SEM). The SEM study of hydrogels on higher magnification revealed a highly porous morphology with uniformly arranged pores ranging from 40 to 200 μm in size. XRD analysis revealed the amorphous nature of the hydrogels, and it was found that an increase in the IA content in the monomer feed greatly reduced the crystallinity of the hydrogels. Swelling experiments were carried out in buffer solutions at different pH values (1.2–10) at 37°C ± 1°C to investigate their pH‐dependent swelling behavior and dimensional stability. An increase in the acid part (IA) increased the swelling ratio of the hydrogels. Temperature‐sensitive swelling of the hydrogels was investigated at 20–70°C in simulated intestinal fluid. The hydrogels swelled at higher temperatures and shrank at lower temperatures. 5‐Aminosalicylic acid (5‐ASA) was selected as a model drug, and release experiments were carried out under simulated intestinal and gastric conditions. 5‐ASA release from the poly N‐[3‐(dimethylamino) propyl] methacrylamide‐co‐itaconic acid‐80 (PDMAPMAIA‐80) hydrogel was found to follow non‐Fickian diffusion mechanism under gastric conditions, and a super case II transport mechanism was found under intestinal conditions. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011