A Thermo‐ and Moisture‐Responsive Zwitterionic Shape Memory Polymer for Novel Self‐Healable Wound Dressing Applications

Developing wound dressings that have strong adhesion strength without causing any conglutination to the wound site is still challenging. Herein, is proposed that zwitterionic shape memory polymers can be applied as promising candidates for wound dressing. Sulfobetaine methacrylate (SBMA) is copolymerized with 2,3‐dihydroxypropyl methacrylate (DHMA) in the presence of boric acid as a cross‐linking agent. The prepared material exhibits multi‐stimuli responsive shape memory behaviors: it can rapidly return to its initial shape upon heating to 90 °C, and a gradual recovery is also observed by absorbing moisture in humid environments. The shape memory effect can be well adjusted via incorporation of sodium chloride to induce the dissociation of electrostatic interactions between PSBMA chains, leading to reduced transition temperature and faster shape recovery rate. Moreover, the dynamic nature of boron ester bonds and electrostatic interaction endows the material with effective and rapid self‐healing ability. It is also demonstrated that the deployment process of the dressing that a sample with an initially circular shape can perfectly fit and tightly bind to the wound site after moisture‐induced shape recovery. The proposed zwitterionic polymer can possibly extend the application scope of shape memory polymers and pave a new way for the design of wound dressings.     

Hyperbranched‐modified epoxy thermosets: Enhancement of thermomechanical and shape‐memory performances

In this study a complete characterization of the thermomechanical and shape‐memory properties of epoxy shape‐memory polymers modified with hyperbranched polymer and aliphatic diamine was performed. Focusing on the mechanical properties that are highly desirable for shape‐memory polymers, tensile behavior until break was analyzed at different temperatures and microhardness and impact strength were determined at room temperature. As regards shape memory performance, the materials were fully characterized at different programming temperatures to study how this influenced the recovery ratio, fixity ratio, shape‐recovery velocity, and switching temperature. Tensile testing revealed a peak in deformability and in the stored energy density at the onset of the glass transition temperature, demonstrating that this is the best programming temperature for obtaining the best shape‐memory performances. The Young's moduli revealed more rigid structures in formulations with higher hyperbranched polymer content, while microhardness showed higher values with increasing hyperbranched polymer content due to the increased crosslinking density. Impact strength was greatly improved as the aliphatic diamine content increases due to the energy dissipation capability of its flexible structure. As regards the shape‐memory properties, increasing the programming temperature has a minor effect on formulations with a lower hyperbranched polymer content and worsens these properties when the hyperbranched polymer content is increased. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44623.     

Synthesis and characterization of temperature‐responsive copolymers based on N‐vinylcaprolactam and their grafting on fibres

BACKGROUND: Responsive materials are able to respond reversibly to an environmental stimulus. When the stimulus is temperature in the physiological range, the responsive material is particularly interesting for textile applications. We describe here the synthesis and characterization of reactive temperature‐responsive copolymers and their subsequent grafting on cotton fabrics. RESULTS: Copolymers of N‐vinylcaprolactam and various reactive monomers were synthesized via free radical polymerization in solution. The copolymers were characterized in terms of chemical structure, molecular weight and temperature‐responsive properties. The copolymer of N‐vinylcaprolactam and methacrylic acid (11 or 22 wt%) and the hydrolysed copolymer of N‐vinylcaprolactam and acryloyl chloride were found to be temperature responsive. They were subsequently grafted on cotton fabrics. The grafting was studied using X‐ray photoelectron spectroscopy and scanning electron microscopy measurements and was found to be effective. Finally, the modified cotton fabrics were found to exhibit temperature‐responsive water regain and water vapour transmission rates. CONCLUSION: Temperature‐responsive copolymers were synthesized, characterized and successfully grafted on cotton fabrics, yielding responsive fabrics. Such fabrics can hence be used to modulate the skin microclimate under textiles. Copyright © 2009 Society of Chemical Industry     

Preparation of quadruple responsive polymeric micelles combining temperature‐, pH‐, redox‐, and UV‐responsive behaviors and its application in controlled release system

A novel series of quadruple responsive copolymers, poly(ethylene glycol)‐ss‐[poly(dimethylaminoethyl methacrylate)‐co‐poly(2‐nitrobenzyl methacrylate)] [PEG‐ss‐(PDMAEMA‐co‐PNBM)], were synthesized via atom transfer radical polymerization mediated by home‐made PEG‐based macro‐initiator labeled with disulfides. The obtained copolymers could self‐assemble in aqueous solution forming micelles with the disulfide bridge linking the hydrophilic coronas (PEG) and the hydrophobic cores (PDMAEMA‐co‐PNBM). Investigation on the resulted micelles indicated that the micelles could respond to various stimuli, that is, temperature, pH, the presence of dithiothreitol (DTT), and UV irradiation. Moreover, the responsive behavior of the micelles depends on the type of stimuli, that is, temperature change causes size change of the micelles, while UV irradiation leads to dissolution of the self‐assembled structures. Such stimulus‐dependent responsive behavior could be applied in smart materials that deal with multi‐tasks or in the construction of complex logic gate. The potential application of the multi‐responsive micelles in cargo release system was also evaluated using Nile Red (NR) as model molecule. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46675.     

Heat‐triggered poly(siloxane‐urethane)s based on disulfide bonds for self‐healing application

Polydimethylsiloxane (PDMS) is one of the most widely employed silicon‐based polymers for its high flexibility, low usage temperature, excellent water resistance, outstanding electrical insulting property, and physiological inert, etc. However, the covalent‐bonded Si? O bonds are unable to heal automatically when damaged, which would result in the failure of the materials and devices. Disulfide bond based polymers show high healing efficiency at moderate temperature and have been investigated intensively. Herein, we report a PDMS‐based polyurethane self‐healing polymer (PDMS‐PU) modified with disulfide bonds, which exhibited a reinforced thermal stability, excellent stretchability, and satisfactory self‐healing ability. The effect of different ratio of PDMS and disulfide bond contents on the elastomer properties was investigated. With the increase of PDMS content, the decomposition temperature of the PDMS‐PU‐3 (332 °C) elastomer with highest content of PDMS was increased by 34 °C compared to PDMS‐PU‐1 (298 °C) with lowest content of PDMS and exhibited a largest elongation at break of 1204%. PDMS‐PU‐1 with highest content of disulfide bond possessed a highest healing efficiency of 97%. The results indicated the PDMS‐PU elastomers can be used as self‐healing flexible substrate for flexible electronics. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46532.     

Electrospinning core‐shell nanofibers for interfacial toughening and self‐healing of carbon‐fiber/epoxy composites

This article reports a novel hybrid multiscale carbon‐fiber/epoxy composite reinforced with self‐healing core‐shell nanofibers at interfaces. The ultrathin self‐healing fibers were fabricated by means of coelectrospinning, in which liquid dicyclopentadiene (DCPD) as the healing agent was enwrapped into polyacrylonitrile (PAN) to form core‐shell DCPD/PAN nanofibers. These core‐shell nanofibers were incorporated at interfaces of neighboring carbon‐fiber fabrics prior to resin infusion and formed into ultrathin self‐healing interlayers after resin infusion and curing. The core‐shell DCPD/PAN fibers are expected to function to self‐repair the interfacial damages in composite laminates, e.g., delamination. Wet layup, followed by vacuum‐assisted resin transfer molding (VARTM) technique, was used to process the proof‐of‐concept hybrid multiscale self‐healing composite. Three‐point bending test was utilized to evaluate the self‐healing effect of the core‐shell nanofibers on the flexural stiffness of the composite laminate after predamage failure. Experimental results indicate that the flexural stiffness of such novel self‐healing composite after predamage failure can be completely recovered by the self‐healing nanofiber interlayers. Scanning electron microscope (SEM) was utilized for fractographical analysis of the failed samples. SEM micrographs clearly evidenced the release of healing agent at laminate interfaces and the toughening and self‐healing mechanisms of the core‐shell nanofibers. This study expects a family of novel high‐strength, lightweight structural polymer composites with self‐healing function for potential use in aerospace and aeronautical structures, sports utilities, etc. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Automated 3D assembly of periodic alumina‐epoxy composite structures

Modular composites with a 3D periodic structure, consisting of a major brittle inorganic phase (building blocks) and a minor viscoelastic organic matrix, offer great potentials for improved fracture toughness and failure probability in polymer‐ceramic composites. Alumina building blocks with dimensions of 1500 μm were assembled by a novel placing system equipped with an automatic optical inspection (AOI) system. The AOI system coupled with shape recognition enables simultaneous dimensional characterization, tolerance sorting, and flexible placing of different shaped building blocks. 3D periodic structures with cubic, monoclinic, and triclinic unit cells were fabricated by high accuracy placing of cubic building blocks enabling near‐net shape manufacturing. The placing precision of the assembled structures was determined by μCT to have a maximum deviation of ±78 μm. The structures were afterward infiltrated with a soft epoxy resin to fabricate epoxy‐alumina composites. The brick‐and‐mortar like building block arrangements of the monoclinic and triclinic structures exhibited improved bending strength, fracture toughness, and failure probability compared to monolithic epoxy, due to crack deflection and pull‐out toughening mechanisms. A maximum bending strength of 35.1 ± 7.5 MPa, a work‐of‐fracture of 814.7 ± 255.1 J/m² and a calculated fracture toughness of 4.8 ± 0.8 MPa for the triclinic structures was achieved.     

Recent advances in flexible sensors for wearable and implantable devices

Flexible devices are emerging as important applications for future display, robotics, in vitro diagnostics, advanced therapies, and energy harvesting. In this review, we provide an overview of recent achievements in flexible mechanical and electrical sensing devices, focusing on the properties and functions of polymeric layers. In the order of historical development, sensing platforms are classified into four types: electronic skins for robotics and medical applications, wearable devices for in vitro diagnostics, implantable devices for human organs or tissues for surgical applications, and advanced sensing devices with additional features such as transparency, self‐power, and self‐healing. In all of these examples, a polymer layer is used as a versatile component including a flexible structural support and a functional material to generate, transmit, and process mechanical and electrical inputs in various ways. We briefly discuss some outlooks and future challenges toward the next steps for flexible devices. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1429–1441, 2013     

Significantly improving electro‐activated shape recovery performance of shape memory nanocomposite by self‐assembled carbon nanofiber and hexagonal boron nitride

This study presents two effective approaches to significantly improve the electro‐thermal properties and electro‐activated shape recovery performance of shape memory polymer (SMP) nanocomposites that are incorporated with carbon nanofibers (CNFs) and hexagonal boron nitrides (h‐BNs), and show Joule heating triggered shape recovery. CNFs were self‐assembled and deposited into buckypaper form to significantly improve the electrical properties of SMP and achieve the shape memory effect induced by electricity. The h‐BNs were either blended into or self‐assembled onto CNF buckypaper to significantly improve the thermally conductive properties and electro‐thermal performance of SMPs. Furthermore, the shape recovery behavior and temperature profile during the electrical actuation of the SMP nanocomposites were monitored and characterized. It was found that a unique synergistic effect of CNFs and h‐BNs was presented to facilitate the heat transfer and accelerate the electro‐activated shape recovery behavior of the SMP nanocomposites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40506.     

Sequential Motion of 4D Printed Photopolymers with Broad Glass Transition

The term “4D printing” refers to the development of stimulus‐responsive structures through 3D printing of active smart materials, typically shape memory polymers. A noteworthy aim of this research field is to obtain objects able to display complex shape‐shifting motions, such as sequential transformations over time. In this work, this peculiar response is studied on a commercial photopolymer, printed by stereolithography and featuring, on the basis of its inherent broad glass transition, the so‐called “temperature‐memory effect” (TME). The TME, that is, a response in which the shape memory effect occurs on a region controlled by the deformation temperature, is studied in shape memory cycles where the deformation temperature is systematically varied, so to provide a correlation between deformation and recovery temperatures. This also allows to properly select two temperatures at which deforming a specimen along a multistep history, so as to finally separate each recovery process on the temperature and time scales. This sequential recovery is studied in double folded bars, with arms deformed at different temperatures, and on a properly designed self‐locking clamp. The obtained results are promising for the realization of smart temperature‐responsive structures printed with one single polymer and capable of multiple shape transformations.     

Surface grafting of carbon fibers with artificial silver‐nanoparticle‐decorated graphene oxide for high‐speed electrical actuation of shape‐memory polymers

Poor heat conduction in the interface between the carbon fiber and polymer matrix is a problem in the actuation of shape‐memory polymer (SMP) composites by Joule heating. In this study, we investigated the effectiveness of grafting silver‐nanoparticle‐decorated graphene oxide (GO) onto carbon fibers to improve the electrothermal properties and Joule‐heating‐activated shape recovery of SMP composites. Self‐assembled GO was grafted onto carbon fibers to enhance the bonding of the carbon fibers with the polymeric matrix via van der Waal's forces and covalent crosslinking, respectively. Silver nanoparticles were further self‐assembled and deposited to decorate the GO assembly, which was used to decrease the thermal dissimilarity and facilitate heat transfer from the carbon fiber to the polymer matrix. The carbon fiber was incorporated with SMP to achieve the shape recovery induced by Joule heating. We found that the silver‐nanoparticle‐decorated GO helped us achieve a more uniform temperature distribution in the SMP composites compared to those without decoration. Furthermore, the shape‐recovery behavior and temperature profile during the Joule heating of the SMP composites were characterized and compared. A unique synergistic effect of the carbon fibers and silver‐nanoparticle‐decorated GO was achieved to enhance the heat transfer and a higher speed of actuation. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41673.     

Amphiphilic polymer co‐networks: 32 years old and growing stronger – a perspective

This brief perspective overviews amphiphilic polymer co‐networks (APCNs), polymeric chemically crosslinked hydrogels also covalently hosting a hydrophobic segment, conferring upon these materials the important property of internal self‐organization in aqueous environments. APCN synthesis is most conveniently accomplished via the random crosslinking copolymerization of a hydrophilic monomer with a hydrophobic macro‐crosslinker, whereas better structures are attained via the end‐linking of amphiphilic linear ABA triblock copolymers or amphiphilic star diblock copolymers. Microphase‐separated morphologies, translucency‐to‐transparency, biocompatibility, low to moderate aqueous swelling, fair mechanical strength and possible stimulus‐responsiveness constitute the main physicochemical properties of APCNs, with their major commercial application being in silicone hydrogel soft contact lenses. Modeling the swelling, morphological and mechanical behavior of these intriguing materials is an area where more progress is necessary in order to improve our understanding of these networks and facilitate the design of next‐generation APCNs. © 2020 Society of Industrial Chemistry     

Metallo‐supramolecular materials based on terpyridine‐functionalized polyhedral silsesquioxane

In this study, novel metallo‐supramolecular materials based on terpyridine‐functionalized polyhedral silsesquioxane were synthesized from 4′‐chloro‐2,2′:6′,2″‐terpyridine and amino‐group‐functionalized polyhedral oligomeric silsesquioxane. The obtained terpyridine‐functionalized polyhedral silsesquioxanes were converted to metallo‐supramolecular hybrid materials by coordination polycondensation reaction with Co(II) or Cu(II) ions. The supramolecular polymers created were characterized by means of structure, morphology and stimuli‐responsive performance employing scanning electron microscopy, amperometric techniques and UV–visible and Fourier transform IR spectroscopy. UV?visible and cyclic voltammetry studies showed that both the optical and electrochemical properties of metallo‐supramolecular materials are affected by the substituent at the pyridine periphery. The supramolecular polymers obtained exhibited electrochromism during the oxidation processes of cyclic voltammogram studies. As a result, these terpyridine‐functionalized polyhedral silsesquioxanes are good candidates for electronic, opto‐electronic and photovoltaic applications as smart stimuli‐responsive materials. © 2013 Society of Chemical Industry     

Highly efficient adsorbent for organic dyes based on a temperature‐ and pH‐responsive multiblock polymer

The self‐assembly behavior of amphiphilic block copolymers in selective solutions has many applications in environmentally responsive polymer materials. In this article, we report on a new amphiphilic, temperature and pH dual‐responsive poly[2‐dimethylaminoethyl methacrylate‐co‐(methyl methacrylate)]‐b‐poly[poly(ethylene glycol) methacrylate] [P(DMAEMA‐co‐MMA)‐b‐PPEGMA], which was synthesized via reversible addition–fragmentation chain‐transfer polymerization. The structure, self‐assembly behaviors, and process of organic dye adsorption were characterized by ¹H‐NMR, ultraviolet–visible absorbance spectroscopy, and DLS measurements. P(DMAEMA‐co‐MMA)‐b‐PPEGMA was proven to be an outstanding adsorbent with excellent reversibility. Methyl red was released from the micelles as the pH value of the solution was adjusted to 4, and it could also be encapsulated again when the pH value was adjusted to 7.4 because of the sensitive pH‐responsive ability. It is promising that the triblock polymer had a positive effect on dye adsorption for environmental protection. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46626.     

Self‐healing properties of layer‐by‐layer assembled multilayers

The review is focused on the formation and the self‐healing properties of polymer and hybrid multilayers formed via the layer‐by‐layer approach. In the first part of the review the recent developments in the construction of polymer multilayers are highlighted. In the second part the design and the self‐healing properties of inorganic ? polymer hybrid multilayers are described. It is shown that self‐healing multilayers have a broad spectrum of applications including corrosion protection, as elements of antifouling and antimicrobial coatings and bio‐inspired superhydrophobic interfaces. It is demonstrated that dynamic functional interfaces have a complex hierarchical organization of non‐covalently bonded polymers and colloidal particles. Mechanisms of self‐healing behavior of the multilayers and the role of water and external stimuli (pH, ionic strength and temperature, light) in swelling of multilayers and rearrangement of polymer segments are discussed. Future trends, perspectives and research strategies for the design of ‘smart’ self‐assemblies with self‐healing properties are proposed. © 2015 Society of Chemical Industry     

A simulation method to analyze chemo‐mechanical behavior of swelling‐induced shape‐memory polymer in response to solvent

A network of thermally responsive shape‐memory polymers (SMPs) could imbibe a quantity of solvent molecules to swell, and subsequently induces a chemical potential change in polymer. When an equilibrium is reached between the mechanical load and the chemical potential of polymer network and solvent, the SMP polymer usually swells with a field of inhomogeneous and anisotropic deformation, which is considered to be equivalent to a hyperelastic field. We implement this theory in the free‐energy function equation, and analyze examples of swelling‐induced deformation and shape recovery behavior. This work may provide a powerful tool to study complex swelling‐induced shape‐memory behavior of SMPs in response to the immersing solvents. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Application of stimuli responsive polymers for sustainable ion exchange chromatography

Ion exchange processes are widely used in the food, bioprocessing and related industries for the isolation of proteins and other ionic species. Traditional ion exchange resins require salts, acids or bases for releasing adsorbed molecules creating a strong saline waste stream with negative environmental and economic impact. Stimuli responsive polymers (SRPs) with ion exchange functional groups can be used to selectively capture and release charged molecules from a complex mixture using physical stimuli to trigger conformational transitions in the polymer. The structural change of the polymers in response to a stimulus may lead to reduced ligand–target molecule interaction resulting in the release of the captured molecule without the use of chemical reagents, thereby reducing the environmental burden associated with ion exchange processes. The use of temperature responsive polymers has already been demonstrated for such applications at analytical scale. However, little progress has been made to extend these discoveries to the development of materials and methods amenable to industrial scale processing. So far, other SRPs such as, electric, magnetic and light responsive polymers remain largely unexplored for such application. This article discusses the potential of temperature responsive and other SRPs for developing sustainable ion exchange processes. It also highlights the material science and engineering challenges that need to be overcome to bring such processes to industrial application.     

Cable‐Shaped Lithium–Sulfur Batteries Based on Nitrogen‐Doped Carbon/Carbon Nanotube Composite Yarns

The research on flexible and wearable devices has attracted extensive attention in the last few years. Lithium–sulfur (Li‐S) batteries are regarded as a promising option because of their high theoretical capacity and energy density. Here, cable‐shaped Li‐S batteries are developed based on a nitrogen‐doped carbon/carbon nanotube/sulfur (NCNT/S) composite cathode and lithium metal anode. The carbon nanotube (CNT) yarns with high conductivity and an appropriate amount of doped nitrogen are synthesized by wet‐spinning followed by a carbonization process, and further act as a self‐supported conductive backbone for the active material. The NCNT/S yarns exhibit a high initial capacitance of 1001 mAh g^?1 and excellent cyclic stability with 87% capacity retention after 200 cycles at 0.5 C. Furthermore, the assembled cable‐shaped Li‐S batteries by NCNT/S yarns present good ability to light up the LEDs for more than 8 h under normal and bending states at various angles, indicating that the cable‐shaped Li‐S batteries could be a prospective candidate for application in wearable electronics.     

Sterilization of Thiol‐ene/Acrylate Based Shape Memory Polymers for Biomedical Applications

A fundamental study on the sterilization of thiol‐ene/acrylate polymers for biomedical applications is presented. These polymer networks belong to the emerging field of shape memory polymers and have the capability to undergo softening after insertion into the body. The impact of various sterilization methods, such as radiation, steam, and ethylene oxide on the thermomechanical properties of these stimuli responsive materials is investigated. Time and temperature dependent thermomechanical properties of sterilized and nonsterilized samples are determined by means of dynamic mechanical analysis in an aqueous environment to allow testing of polymers in phosphate buffered saline. The findings show that ethylene oxide sterilization is appropriate for thiol‐ene and thiol‐ene/acrylate based shape memory polymers. This method does not adversely affect thermomechanical and self‐softening properties and after sterilization, endotoxin levels remain below the thresholds recommended in the FDA Guidance.

     

Zein‐based micro‐ and nano‐particles for drug and nutrient delivery: A review

Zein is the major storage protein from corn with strong hydrophobicity and unique solubility and has been considered as a versatile food biopolymer. Due to the special tertiary structures, zein can self‐assemble to form micro‐ and nano‐particles through liquid–liquid dispersion or solvent evaporation approaches. Zein‐based delivery systems have been particularly investigated for hydrophobic drugs and nutrients. Recently, increasing attention has been drawn to fabricate zein‐based advanced drug delivery systems for various applications. In this review, the molecular models of zein tertiary structure and possible mechanisms involved in zein self‐assembly micro‐ and nano‐particles are briefly introduced. Then, a state‐of‐the‐art introduction and discussion are given in terms of preparation, characterization, and application of zein‐based particles as delivery systems in the fields of food science, pharmaceutics, and biomedicine. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40696.