Mechanically tough dry-free ionic hydrogel microfibers swollen in aqueous electrolyte prepared by microfluidic devices

Soft conducting materials in the shape of microfibers with various functional geometries are crucial for soft electronics. To develop highly stretchable conducting microfibers, a microfluidic method is used to prepare hydrogels in a double-network structure. Based on the coagulation of chitosan in cold water and simultaneous photopolymerization and photocrosslinking of N-isopropylacrylamide and N-diethylacrylamide, long microfibers with controlled uniform diameters can be obtained at the junction of a coaxially aligned microchannel device. After further reinforcement of the chitosan chain and exchange of the medium of the hydrogel microfiber with an aqueous electrolyte of lithium bis(trifluoromethanesulfonyl)imide, the prepared ionic hydrogel exhibits high conductivity and stretchability and dry-free properties. Owing to its mechanical robustness and ionic conductivity, we envision a highly stretchable soft electrode with the prepared ionic hydrogel microfiber that can be stretched up to 900%. This fiber has potential for applications in soft electronics and wearable devices.     

Stretchable and transparent hydrogels as soft conductors for dielectric elastomer actuators

A soft ionic conductor can serve as an artificial nerve in an artificial muscle. A polyacrylamide hydrogel is synthesized containing a hygroscopic salt, lithium chloride. Two layers of the hydrogel are used as ionic conductors to sandwich a dielectric elastomer and fabricate a highly stretchable and transparent actuator. When the two layers of the hydrogels are subject to a voltage, the actuator reduces its thickness and expands. An areal strain of 134% is demonstrated. The voltage‐strain curves are calculated by using a model that accounts for the elastic constraint of the hydrogel and the inhomogeneous deformation of the actuator. For actuators fabricated with the hydrogel of various thicknesses and with the dielectric elastomer of various prestretches, excellent agreements are found between experimental data and theoretical predictions. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1055–1060     

Tailoring 3D hydrogel systems for neuronal encapsulation in living electrodes

State‐of‐the‐art neurorprostheses rely on stiff metallic electrodes to communicate with neural tissues. It was envisioned that a soft, organic electrode coating embedded with functional neural cells will enhance electrode‐tissue integration. To enable such a device, it is necessary to produce a cell scaffold with mechanical properties matched to native neural tissue. A degradable poly(vinyl alcohol) (PVA) hydrogel was tailored to have a range of compressive moduli through variation in macromer composition and initiator amount. A regression model was used to predict the amount of initiator required for hydrogel polymerization with nominal macromer content ranging between 5 and 20 wt %. Hydrogels at 5 and 10 wt % were reliably formed but 15 wt % and above were not able to be fabricated due to the light attenuation properties of the initiator ruthenium at increased concentration. Compressive modulus of hydrogels decreased upon incorporation of biomolecules (sericin and gelatin), however, the bulk stiffness spanned the range required to match neural tissue properties (0.04–20kPa). Neuroglia cells, such as Schwann cells survived and grew within the scaffold. The significant finding of this work is that the PVA‐tyramine system can be tuned to provide a soft degradable scaffold for neural tissue regeneration while presenting bioactive molecules for cellular expansion. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 273–287     

Thermal actuation of hydrogels from PNIPAm,alginate, and carbon nanofibres

Composite ionic‐covalent entanglement (ICE) hydrogel networks were prepared from poly(N‐isopropylacrylamide), alginate, and carbon nanofibres. An optimised triple network hydrogel with 86% water content exhibited a compressive strength of 3.0 ± 0.1 MPa and 66 ± 13 mS/cm electrical conductivity. Thermal actuation was shown to have a shorter response time for gels containing nanofibres, compared to those which did not and hydrogel samples more than halved in volume within 1 minute when placed in a 60 °C water bath. Controlled dye release was demonstrated as a potential application and used to further quantify thermal actuation over short times. Joule heating techniques were used to electronically actuate the hydrogel samples, removing the traditional requirements for immersion in a temperature controlled liquid. It is expected that devices based on these materials will find potential applications in soft robotics and micro fluidics. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 46–52     

Imine‐based dynamic polymer networks as photoprogrammable amine sensing devices

Here, we describe a “smart” polymeric material, which is able to readily detect and discriminate amine vapors. The dynamic imine‐based network can be conveniently prepared by mixing a commercially available, amino‐functionalized polysiloxane with small amounts of a diarylethene dialdehyde. The photoswitchable crosslinker allows for reversible imprinting of custom‐designed patterns on the polymer surface with (sun)light and thus enables noninvasive information storage in the material, which before, during, and after amine exposure can readily be decoded with commonly used smartphone apps. This feature along with the self‐healing nature of the dynamic polymer, an easy recycling and manufacturing procedure, and the overall low cost and toxicity render this material advantageous to develop low‐cost and practical amine sensing devices for the broad public. © 2019 The Authors. Journal of Polymer Science Part A: Polymer Chemistry published by Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 2378–2382     

Cross‐linking induced thermoresponsive hydrogel with light emitting and self‐healing property

Development of self‐healing hydrogels with thermoresponse is very important for artificial smart materials. In this article, the self‐healing hydrogels with reversible thermoresponses were designed through across‐linking‐induced thermoresponse (CIT) mechanism. The hydrogels were prepared from ketone group containing copolymer bearing tetraphenyl ethylene (TPE) and cross‐linked by naphthalene containing acylhydrazide cross‐linker. The mechanical property, light emission, self‐healing, and thermo‐response of the hydrogels were investigated intensively. With regulation of the copolymer composition, the hydrogels showed thermoresponse with the LCST varied from above to below body temperature. At the same time, the hydrogels showed self‐healing property based on the reversible characteristic of the acylhydrazone bond. The hydrogel also showed temperature‐regulated light emission behavior based on AIE property of the TPE unit. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 869–877     

Double‐crosslinked reversible redox‐responsive hydrogels based on disulfide–thiol interchange

We present novel redox‐responsive hydrogels based on poly(N‐isopropylacrylamide) or poly(acrylamide), consisting of a reversible disulfide crosslinking agent N,N′‐bis(acryloyl)cystamine and a permanent crosslinking agent N,N′‐methylenebisacrylamide for microfluidic applications. The mechanism of swelling/deswelling behavior starts with the cleavage and reformation of disulfide bonds, leading to a change of crosslinking density and crosslinking points. Raman and ultraviolet‐visible spectroscopy confirm that conversion efficiency of thiol–disulfide interchange up to 99%. Rheological analysis reveals that the E modulus of hydrogel is dependent on the crosslinking density and can be repeatedly manipulated between high‐ and low‐stiffness states over at least 5 cycles without significant decrease. Kinetic studies showed that the mechanical strength of the gels changes as the redox reaction proceeds. This process is much faster than the autonomous diffusion in the hydrogel. Moreover, cooperative diffusion coefficient (D_coop) indicates that the swelling process of the hydrogel is affected by the reduction reaction. Finally, this reversibly switchable redox behavior of bulky hydrogel could be proven in microstructured hydrogel dots through short‐term photopatterning process. These hydrogel dots on glass substrates also showed the desired short response time on cyclic swelling and shrinking processes known from downsized hydrogel shapes. Such stimuli‐responsive hydrogels with redox‐sensitive crosslinkers open a new pathway in exchanging analytes for sensing and separating in microfluidics applications. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 2590–2601     

Environmentally Stable Polymer Gels with Super Deformability and High Recoverability Enhanced by Sub‐5 nm Particles in the Nonvolatile Solvent

It remains challenging to satisfy the combined performances for hydrogels with excellent mechanical behavior, high deformability, and super recoverability under harsh environmental conditions. In this study, we first established a strong polymer network via the crosslinking of polymer chains on the surfaces of sub‐5‐nm calcium hydroxide nanospherulites in ethylene glycol solvent. The organic gel expressed excellent mechanical properties such as a recoverable compressive engineering stress of 249 MPa and an elongation stress of 402 KPa, which was attributed to the uniform nanosized crosslinking structure as characterized by SEM. Moreover, the nonvolatile solvent remained in the gel, meaning that the sample can resist a wide temperature range of ?56 to 100 °C without losing the elastic properties. This novel organic gel could provide promising routes to develop the ideal elastic carriers for wearable devices, smart skin sensors, and damping materials. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 713–721     

Charge‐Functionalized and Structurally Enhanced (Cryo)Hybrids from Acrylic (Co)Monomers and Kaolin: Altering Physicochemical Properties via Cryotropic Gelation

The potential to improve mechanical, structural, and mechanochemical properties of charge‐functionalized poly(N,N‐dimethylaminoethyl methacrylate) (PDMAEMA)‐based hybrid cryogels is investigated. The simple and versatile synthesis of hybrid cryogels with high strength and toughness using cationic DMAEMA and ionic comonomer 2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid has been proposed via in situ free‐radical crosslinking (cryo)polymerization by which the properties of virgin polymer can be modulated to required applications by incorporation of inorganic filler kaolin (KLN). Two factors affecting swelling and elasticity of hybrid gels (referred as PDA/KLNm), KLN content and gel preparation temperature, are studied. The optimum KLN concentration for desired swelling and modulus of elasticity is determined as 0.80% (w/v). Effective crosslinking density of hybrid hydrogels increases with KLN addition and this dependence is expressed by a quadratic polynomial as a function of KLN concentration. The results show that obtained hybrid gels with multiresponsive properties could be regarded as “smart materials” in sensing and actuation applications. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1758–1778     

Reverse mode operation polymer dispersed liquid crystal with a positive dielectric anisotropy liquid crystal

The development of electrically activated chromogenic materials is important for their potential applications in smart windows. Several previous works have reported on reverse mode operation polymer dispersed liquid crystals (PDLCs) based on negative dielectric anisotropy liquid crystals. They have a transparent OFF state, which turns opaque after the application of a suitable external electric field. Nevertheless, these devices have some limitations such as the use of large amount of expensive liquid crystals with peculiar physical‐chemical properties. In addition, a good matching between the refractive index of liquid crystal and the polymer matrix one is required. The main result of this work is the achievement of reverse mode operation devices prepared with a positive dielectric anisotropy liquid crystal and characterized by a high OFF state transmittance obtained by the onset of high intensity built‐in DC electric fields in a direct mode operation PDLC, which allows the OFF state homeotropic alignment of liquid crystal directors. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Poly(l‐glutamic acid)‐based micellar hydrogel with improved mechanical performance and proteins loading

Soft tissues, such as fat and skin, present high flexibility and are capable of withstanding large deformation in various functions. Hydrogels that can resemble the mechanical performance of soft tissue are unique and widely demanded. In this study, micellar hydrogels based on biocompatible poly(l ‐glutamic acid) (PLGA) were designed with the enhanced capacity to bear large deformation. Amphipathic triblock copolymer poly(ethylene glycol) acrylate‐co‐poly(ε‐caprolactone)‐co‐poly (ethylene glycol) acrylate (APEG‐PCL‐APEG) with two terminal double bonds was synthesized and self‐assembled into micelles. At the same time, graft copolymers, poly(l ‐glutamic acid)‐g‐hydroxyethyl methacrylate (PLGA‐g‐HEMA) with double bonds were synthesized. APEG‐PCL‐APEG micelles and PLGA‐g‐HEMA were mixed to construct micellar hydrogel via radical polymerization. The crystalline structure and hydrophobic aggregation of copolymers (APEG‐PCL‐APEG) were found to associate with PCL molecular weight. Due to the hydrophobic stress dissipation and crystalline structure of the micelles, the softness and toughness of hydrogels were promoted, exhibiting a 25% increase in ultimate strain. Moreover, the micellar hydrogels were able to load proteins with long‐term retention. In addition, under dynamic mechanical stimulation, the release of proteins could be accelerated. Besides, the micellar hydrogels also supported rabbit adipose‐derived stem cells (rASCs) growth, thus exhibiting the potential toward soft tissue engineering. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1115–1125     

Thermoresponsive hydrogel of poly(glycidyl methacrylate‐co‐N‐isopropylacrylamide) as a nanoreactor of gold nanoparticles

The synthesis of a thermoresponsive hydrogel of poly(glycidyl methacrylate‐co‐N‐isopropylacrylamide) (PGMA‐co‐PNIPAM) and its application as a nanoreactor of gold nanoparticles are studied. The thermoresponsive copolymer of PGMA‐co‐PNIPAM is first synthesized by the copolymerization of glycidyl methacrylate and N‐isopropylacrylamide using 2,2′‐azobis(isobutyronitrile) as an initiator in tetrahydrofuran at 70 °C and then crosslinked with diethylenetriamine to form a thermoresponsive hydrogel. The lower critical solution temperature (LCST) of the thermoresponsive hydrogel is about 50 °C. The hydrogel exists as 280‐nm spheres below the LCST. The diameter of the spherical hydrogel gradually decreases to a minimum constant of 113 nm when the temperature increases to 75 °C. The hydrogel can act as a nanoreactor of gold nanoparticles because of the coordination of nitrogen atoms of the crosslinker with gold ions, on which a hydrogel/gold nanocomposite is synthesized. The LCST of the resultant hydrogel/gold nanocomposite is similar to that of the hydrogel. The size of the resultant gold nanoparticles is about 15 nm. The hydrogel/gold nanocomposite can act as a smart and recyclable catalyst. At a temperature below the LCST, the thermoresponsive nanocomposite is a homogeneous and efficient catalyst, whereas at a temperature above the LCST, it becomes a heterogeneous one, and its catalytic activity greatly decreases. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2812–2819, 2007     

Synthesis of n‐alkyl methacrylate polymers with pendant carbazole moieties and their derivatives

New methacrylate monomers with carbazole moieties as pendant groups were synthesized by multistep syntheses starting from carbazoles with biphenyl substituents in the aromatic ring. The corresponding polymers were prepared using a free‐radical polymerization. The novel polymers contain N‐alkylated carbazoles mono‐ or bi‐substituted with biphenyl groups in the aromatic ring. N‐alkyl chains in polymers vary by length and structure. All new polymers were synthesized to evaluate the structural changes in terms of their effect on the energy profile, thermal, dielectric, and photophysical properties when compared to the parent polymer poly(2‐(9H‐carbazol‐9‐yl)ethyl methacrylate). According to the obtained results, these compounds may be well suited for memory resistor devices. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 70–76     

Hydrogel‐coated polyurethane/urea shape memory polymer foams

Shape memory polymers (SMPs) are a class of responsive polymers that have attracted attention in designing biomedical devices because of their potential to improve minimally invasive surgeries. Use of porous SMPs in vascular grafts has been proposed because porosity aids in transfer of fluids through the graft and growth of vascular tissue. However, porosity also allows blood to leak through grafts so preclotting the materials is necessary. Here hydrogels have been synthesized from acrylic acid and N‐hydroxyethyl acrylamide and coated around a porous SMP produced from lactose functionalized polyurea‐urethanes. The biocompatibility of the polymers used to prepare the cross‐linked shape memory material is demonstrated using an in vitro cell assay. As expected, the hydrogel coating enhanced fluid uptake abilities without hindering the shape memory properties. These results indicate that hydrogels can be used in porous SMP materials without inhibiting the shape recovery of the material. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1389–1395     

Nanocomposite smart hydrogels with improved responsiveness and mechanical properties: A mini review

Responsive hydrogels have the ability to change their volume, transparency, or other properties in response to external chemical and/or physical stimuli. The responsiveness properties including responsive rate and degree, as well as mechanical properties such as Young's modulus, toughness, breaking strength, and breaking strain are crucial parameters of the smart hydrogels that determine the scope of hydrogel applications such as soft actuators, artificial muscles, and tissue engineering scaffolds. In this paper, the development of the nanocomposite smart hydrogels, which can achieve both improved responsiveness and mechanical properties, is reviewed. First, the fabrication approaches for building the nanocomposite networks by doping organic or inorganic nanomaterials via crosslinking or blending strategies are introduced. Then, the mechanisms used to improve both responsiveness and mechanical properties of nanocomposite responsive hydrogels are discussed. Finally, the perspectives as well as current challenges of such nanocomposite responsive hydrogels are addressed. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 1306–1313     

4D Printing based piezoelectric composite for medical applications

Additive manufacturing (AM), otherwise known as three‐dimensional (3D) printing, is driving major innovations in many areas, such as engineering, manufacturing, art, education, and medicine. Although a considerable amount of progress has been made in this field, additional research work is required to overcome various remaining challenges. Recently, one of the actively researched areas lies in the AM of smart materials and structures. Electroactive materials incorporated in 3D printing have given birth to 4D printing, where 3D printed structures can perform as actuating and/or sensing systems, making it possible to deliver electrical signals under external mechanical stimuli and vice versa. In this paper, we present a lightweight, low cost piezoelectric material based on the dispersion of inorganic ferroelectric submicron particles in a polymer matrix. We report on how the proposed material is compatible with the AM process. Finally, we discuss its potential applications for healthcare, especially in smart implants prostheses. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 109–115     

Stress memory polymers

Like shape memory polymers, a novel phenomenon of stress memory was shown in which the stress of a material can respond to an external stimulus. This concept was further enlightened by a switch‐spring‐frame model that would eliminate the limitation of existing models which overlooked the stimulus responsive nature of such polymers. The discovery being reported in this article was stemmed from a real case study into shape memory polymer fibers in compression stocking for varicose veins. The breakthrough of stress memory enabled researchers to develop applications needing stimuli‐responsive forces, which can broaden the horizon of such smart polymers in emerging smart products in many multidisciplinary fields such as sensors, stress garments, and massage devices, electronic skins, and artificial muscles. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 893–898     

Zr(IV)‐Crosslinked Polyacrylamide/Polyanionic Cellulose Composite Hydrogels with High Strength and Unique Acid Resistance

Recently, metal coordination has been widely utilized to fabricate high‐performance hydrogels, but conventional metal‐based hydrogels face some drawbacks, such as staining or acid lability. In the present study, a novel kind of colorless Zr(IV)‐crosslinked polyacrylamide/polyanionic cellulose (PAM/PAC) composite hydrogel with unique acid resistance was constructed via acrylamide polymerization in a PAC solution, followed by posttreatment in a zirconium oxychloride (ZrOCl₂) solution. The prepared gels were characterized in terms of Fourier transform infrared spectroscopy, scanning electron microscopy, and tensile and compressive mechanics, as well as acid resistance. Inside the gels, the synergistic action of hydrogen bonding and Zr(IV) coordination is responsible for their improved mechanical properties and good energy dissipation ability. One hydrogel with nearly 90 wt % of water content can sustain approximately 5 MPa of compression stress at 90% strain without damage. Both microscopic network structures and macroscopic mechanics demonstrate facile adjustability via changing the PAC dosages in polymerization and/or ZrOCl₂ concentrations in posttreatment. Moreover, the gels present unexpected acid resistance due to the strong Zr(IV) coordination with PAC, demonstrating their potential application as hydrogel electrolytes in supercapacitors. The current work provides a new approach to fabricate metal coordination‐based high strength, colorless hydrogels with acid resistance. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 981–991     

Mechanical and electrical response variation of the polyurethane–tin oxide–carbon nanotube composite microfiber depending on the chemical solution

Toward the goal of smart sensor systems for wearable electronics, polymer microfiber‐based free‐standing sensors benefit from excellent flexibility, decent ductility, and easy wearability in comparison with thin‐film‐based sensing devices. Herein, we report a hydrophobic and conducting single‐strand microfiber‐based liquid‐phase chemical sensor consisting of polyurethane (PU), tin oxide (SnO₂), and carbon nanotube (CNT) composites with applying a (1H,1H,2H,2H‐heptadecafluorodec‐1‐yl) phosphonic acid (HDF‐PA)‐based self‐assembled monolayer. The free‐standing HDF‐PA‐treated PU–SnO₂–CNT composite microfiber showing selective filtering properties with the repellency of water and the penetration of an organic solvent is electrically and mechanically characterized. Finally, the single‐strand HDF‐PA‐treated PU–SnO₂–CNT composite microfiber‐based chemical sensor, which shows excellent mechanical properties and aqueous stability, is demonstrated to detect the presence of a chemical in pure water or counterfeit gasoline in pure gasoline by observing mechanical changes, especially variations in the length and diameter of the fiber, and monitoring the electrical resistance change. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 495–502     

Determining thermo‐mechanical properties of polydimethylsiloxanes from their strain‐induced spectral fingerprints

Adaptive properties and complex shapes of modern day soft matter components create a challenge for materials applications where mechanical properties of intricate fabricated components cannot be determined from conventional invasive and destructive mechanical tests. In particular, challenges arising from variable mechanical properties of polydimethylsiloxanes (PDMSs) constantly attract wide‐scale attention in the fields of material sciences, biological systems, and microfluidics. Herein, a noninvasive and nondestructive strain‐induced infrared spectroscopic method (S‐FTIR) is developed. S‐FTIR is a method that maps thermo‐mechanical response of PDMS to its strain‐induced spectral fingerprint. From the results of this study, strong correlations of up to 95% between spectral fingerprint of PDMS and its corresponding nonlinear thermo‐mechanical response is seen. Given the nature of these results, it is expected that S‐FTIR will provide an interesting new analytical approach to understand soft materials and allow for the characterization of micro and nanoscale devices composed of these polymeric materials as well. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 359–367