Inkjet Printing Based Layer‐by‐Layer Assembly Capable of Composite Patterning of Multilayered Nanofilms

Surface modification involves developing a versatile thin film by combining the physical, chemical, or biological characteristics of the functional materials and can facilitate controlling material for desirable aims. Layer‐by‐layer (LbL) assembly can be used to create materials with controlled thicknesses and morphologies, diverse functionalities, and unique structures on any surface. However, despite the advantages of the LbL fabrication technique, there are limits to its application because it is a time‐consuming process and has difficulty controlling the shape of nanofilms. In addition, controlling the lateral organization is difficult because the preparation methods are based on one‐pot self‐assembly. In this study, a multilayered fabrication system is developed for the high‐throughput LbL assembly of nanofilms through inkjet printing. With various types of materials from synthetic polymer to graphene oxide to natural polymer and protein, the approach can tune the preparation of nanoscale multilayers with desired structures and shapes for specific applications on various substrates, including a silicon wafer, quartz glass, and cellulose‐based paper.     

Electric‐field‐induced layer‐by‐layer fabrication of stable second‐order nonlinear optical films

BACKGROUND: Second‐order nonlinear optical (NLO) films have been made using electric field poling polymer and Langmuir–Blodgett techniques with non‐centrosymmetric structures that exhibit relatively high values of nonlinear susceptibility (χ²), but the shortcomings of insufficient temporal or mechanical stability have restricted their potential applications. In this study, electric‐field‐induced layer‐by‐layer assembly was investigated as an effective technique to prepare low molecular weight chromophoric (LMWC) molecules of high degree of self‐ordering and density in NLO films. RESULTS: A new and stable LMWC molecule, 2‐({4‐[4‐(2‐carboxy‐2‐cyanovinyl)‐Z‐phenylazo]‐phenyl}‐methylamino)‐ethyl acid (DRCB), was first designed and synthesized successfully. The chromophore possesses two negative groups, one at each end, and still retains molecular polarity after ionization. DRCB was successfully assembled with polycationic diazoresin using the electric‐field‐induced layer‐by‐layer assembly method to construct stable organic second‐order NLO multilayer films. Upon UV irradiation, the interaction between multilayers was converted from an electrostatic interaction to covalent bonds. CONCLUSION: Due to the DC electric field effect in the assembly process, in addition to introducing the stable chromophore molecule and the covalent crosslinking structure in the films, the second‐order NLO films fabricated using the method described have large second harmonic generation response, good thermal stability and excellent chemical stability, which offer potential advantages for device applications. Copyright © 2009 Society of Chemical Industry     

Polymer clay self‐assembly complexes on paper

Layer‐by‐layer (LBL) self‐assembly was used to form polymer/clay complexes on paper to enhance its wet strength properties. Initially, alternating layers of poly(allylamine hydrochloride) (PAH) and Kaolin clay were sequentially deposited on quartz substrate and characterized by UV/Vis/NIR spectroscopy as a model system. The same procedure was then applied to a paper test sheet to form multilayered coatings, which were examined with scanning electron microscopy. The wettability of the LBL coated paper test sheet was shown to change from hydrophilic to hydrophobic with increased number of multilayers and if the terminating layer was Kaolin clay. The wet strength of the coated test sheet was improved by more than 270% over the uncoated test sheet with 16 bilayers of PAH/kaolin complex on the surface. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

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     

Dynamic layer‐by‐layer self‐assembly of organic–inorganic composite hollow fiber membranes

Multilayer membranes constructed layer‐by‐layer (LbL) is finding increasing importance in many separation applications. The efficient construction of LbL multilayer on to hollow fiber substrates may offer many new opportunities for industrial applications. An organic–inorganic composite hollow fiber membrane has been developed using a dynamic LbL self‐assembly. This poly(acrylic acid)/poly(ethyleneimine) multilayer was dynamically assembled onto the inner surfaces of ceramic hollow fiber porous substrates pretreated by Dynasylan Ameo silane coupling agents. The hollow fibers were subsequently heat crosslinked to obtain stable permselective membranes. The formation of multilayers on the hollow fibers was characterized with a SEM, EDX, an electrokinetic analyzer and IR spectra. The effects of layer number, feed temperature and water content in the feed on the pervaporation performance have been investigated. To the best of our knowledge, this is the first report of LbL assembly of polymer building blocks onto ceramic hollow fiber porous substrates. © 2011 American Institute of Chemical Engineers AIChE J, 58: 3176–3182, 2012     

Flexible Sandwich Structural Strain Sensor Based on Silver Nanowires Decorated with Self‐Healing Substrate

Flexible and stretchable conducting composites that can sense stress or strain are needed for several emerging fields including human motion detection and personalized health monitoring. Silver nanowires (AgNWs) have already been used as conductive networks. However, once a traditional polymer is broken, the conductive network is subsequently destroyed. Integrating high pressure sensitivity and repeatable self‐healing capability into flexible strain sensors represents new advances for high performance strain sensing. Herein, superflexible 3D architectures are fabricated by sandwiching a layer of AgNWs decorated self‐healing polymer between two layers of polydimethylsiloxane, which exhibit good stability, self‐healability, and stretchability. For better mechanical properties, the self‐healing polymer is reinforced with carbon fibers (CFs). The sensors based on self‐healing polymer and AgNWs conductive network show high conductivity and excellent ability to repair both mechanical and electrical damage. They can detect different human motions accurately such as bending and recovering of the forearm and shank, the changes of palm, fist, and fingers. The fracture tensile stress of the reinforced self‐healing polymer (9 wt% CFs) is increased to 10.3 MPa with the elongation at break of 8%. The stretch/release responses under static and dynamic loads of the sensor have a high sensitivity, large sensing range, excellent reliability, and remarkable stability.     

Microwave‐Assisted Reversible Coordination‐Mediated Polymerization for Self‐Healing Hybrid Materials: RGO@PDA Simultaneous as Catalyst and Nanocomposites in One‐Pot

In this article, polydopamine (PDA) is efficiently adhered on the surface of graphene oxide (GO) by mussel‐inspired chemistry. The obtained reduced GO/PDA (RGO@PDA) nanocomposites are used for catalyzing reversible coordination‐mediated polymerization under microwave radiation. Well‐defined and iodine‐terminated polyacrylonitrile‐co‐poly(n‐butyl acrylate) (PAN‐co‐PnBA) is successfully fabricated by using RGO@PDA nanocomposites as catalysts. Importantly, green and novel strategy of PAN‐co‐PnBA‐type self‐healing nanocomposite materials is further fabricated with RGO@PDA as additive after polymerization as catalyst in one‐pot. As a reinforcement agent, RGO@PDA can also improve the mechanical and self‐healing properties of hybrid materials, which opens up a novel and green methodology for the preparation of self‐healing hybrid materials.     

Synthesis,characterization, and self‐assembly of cationic coumarin side‐chain polymer

In this study, the synthesis of a novel cationic coumarin‐containing polymer (C‐CPA) was presented. C‐CPA was examined optically using photoluminescence (PL) spectroscopy. The optical data suggested that they were promising blue‐emitting materials mainly due to the coumarin chromophore on the side chain. Moreover, the synthesized cationic polymer was suitable for layer‐by‐layer electrostatic self‐assembly thin film deposition from dilute polymer solution and multilayers were fully characterized by UV–vis spectroscopy, PL spectroscopy and atomic force microscope. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

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

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

pH‐ and temperature‐induced release of doxorubicin from multilayers of poly(2‐isopropyl‐2‐oxazoline) and tannic acid

We present a simple strategy to prepare doxorubicin (DOX) containing hydrogen‐bonded films of poly(2‐isopropyl‐2‐oxazoline) (PIPOX) and tannic acid (TA) which release DOX in acidic conditions while releasing a minimal amount of DOX at physiological pH. Water soluble complexes of TA and DOX (TA ? DOX) were prepared prior to film construction. PIPOX and TA ? DOX were deposited at the surface at pH 6.5 using the layer‐by‐layer (LbL) technique. We found that multilayers released a minimal amount of DOX at physiological pH due to further ionization of TA with increasing pH and enhanced electrostatic interactions between TA and DOX. In contrast, pH‐induced release of DOX was observed in moderately acidic conditions due to protonation of TA as the acidity increased and electrostatic interactions between TA and DOX decreased. Moreover, we found that raising the temperature from 25 °C to 37.5 °C increased the amount of DOX released from the surface. This can be rationalized with the conformational changes within the multilayers correlated with the lower critical solution temperature behaviour of PIPOX and increased kinetic energy of DOX molecules. Considering the acidic nature of tumour tissues and important biological properties of PIPOX and TA, these multilayers are promising for pH‐ and temperature‐triggered release of DOX from surfaces. © 2017 Society of Chemical Industry     

Flexible Polysaccharide Hydrogel with pH‐Regulated Recovery of Self‐Healing and Mechanical Properties

A self‐healable hydrogel with recoverable self‐healing and mechanical properties is reported. The hydrogel (coded as ACSH) crosslinked by Schiff base linkage contains two polysaccharides of acrylamide‐modified chitosan (AMCS) and oxidized alginate (ADA). Self‐healing and mechanical properties are heavily influenced by the crosslinking time. The hydrogel crosslinked for 2 h possesses better mechanical and self‐healing properties than hydrogel crosslinked for 24 h. Macroscopic test shows that hydrogel without self‐healing ability can recover the self‐repair and mechanical properties by adjusting the pHs. The recovery of self‐healing and mechanical properties relies on the pH sensitivity of the Schiff base linkage. Adjusting the pH to acid, the Schiff base linkage becomes unstable and breaks. Regulating the pH to neutral, reconstruction of Schiff base linkage leads to recovery of the self‐repair and mechanical properties. The recoverable self‐healing property can be cycled once breakage and reconstruction of the Schiff base linkage can be conducted. In addition, this study demonstrates that the hydrogel can be remodeled into different shapes based on self‐healing property of the hydrogel. It is anticipated that this self‐healable hydrogel with recoverable self‐healing and mechanical properties may open a new way to investigate self‐healing hydrogel and find potential applications in different biomedical fields.     

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

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

Recent progress in interfacial toughening and damage self‐healing of polymer composites based on electrospun and solution‐blown nanofibers: An overview

In this article, we provide an overview of recent progress in toughening and damage self‐healing of polymer–matrix composites (PMCs) reinforced with electrospun or solution‐blown nanofibers at interfaces with an emphasis on the innovative processing techniques and toughening and damage self‐healing characterization. Because of their in‐plane fiber architecture and layered structure, high‐performance laminated PMCs typically carry low interfacial strengths and interlaminar fracture toughnesses in contrast to their very high in‐plane mechanical properties. Delamination is commonly observed in these composite structures. Continuous polymer and polymer‐derived carbon nanofibers produced by electrospinning, solution blowing, and other recently developed techniques can be incorporated into the ultrathin resin‐rich interlayers (with thicknesses of a few to dozens of micrometers) of these high‐performance PMCs to form nanofiber‐reinforced interlayers with enhanced interlaminar fracture toughnesses. When incorporated with core–shell healing‐agent‐loaded nanofibers, these nanofiber‐richened interlayers can yield unique interfacial damage self‐healing. Recent experimental investigations in these topics are reviewed and compared, and recently developed techniques for the scalable, continuous fabrication of advanced nanofibers for interfacial toughening and damage self‐healing of PMCs are discussed. Developments in the near future in this field are foreseen. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2225–2237, 2013     

Self‐Healing Latex Containing Polyelectrolyte Multilayers

Self‐healing paints would have the potential benefit of protecting the underlying substrate and extending the coating's service life. As a step toward those types of coatings, this work examines layer‐by‐layer films of branched poly(ethylene imine)/poly(acrylic acid) with the inclusion of various types of latex particles with different T_g and different compositions. Due to high mobility of the polyelectrolyte chains when plasticized with water, water enabled self‐healing of these films is demonstrated, as well as steam enabled self‐healing. The films with various latex particles show different swelling ratios, surface hydrophilicity, as well as varying ability to self‐heal scratches. This self‐healing property is studied as a function of temperature. Also, the mechanical properties such as hardness and modulus of the films are measured.     

Self‐assembly of novel architectural nanohybrid multilayers and their selective separation of solvent‐water mixtures

A new architectural nanohybrid multilayer has been explored and built on various substrates. The building blocks of positive and negative charged polyelectrolyte‐coated nanoparticles (NPs) could be obtained by tuning the electrical properties of the amphoteric oxide NPs in acid and basic environments. The nanohybrid films were, thereafter, formed by layer‐by‐layer (LbL) assembly of polycation‐ and polyanion‐coated NPs. It was demonstrated that this approach could incorporate single component NPs into both polycation and polyanion layers, and in turn improve the NP loading, maintain good dispersion of NPs within the film. For separation applications, a dynamic LbL assembly was attempted as a means of fabricating such nanohybrid multilayers on both 2‐D and 3‐D polymeric porous substrates. The nanohybrid multilayer membrane renders both much higher selectivity and flux in the separation of solvent‐water mixtures. Moreover, such assembly of nanohybrid multilayers allows us to efficiently simplify the procedures by reducing 30–40‐fold process cycles. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

Adaptive Polymeric Coatings with Self‐Reporting and Self‐Healing Dual Functions from Porous Core–Shell Nanostructures

In biological system, early detection and treatment at the same moment is highly required. For synthetic materials, it is demanding to develop materials that possess self‐reporting of early damage and self‐healing simultaneously. This dual function is achieved in this work by introducing an intelligent pH‐responsive coatings based on poly(divinylbenzene)‐graft‐poly(divinylbenzene‐co‐methacrylic acid) (PDVB‐graft‐P(DVB‐co‐AA)) core–shell microspheres as smart components of the polymer coatings for corrosion protection. The key component, synthesized PDVB‐graft‐P(DVB‐co‐AA) core–shell microspheres are porous and pH responsive. The porosity allows for encapsulation of the corrosion inhibitor of benzotriazole and the fluorescent probe, coumarin. Both loading capacities can be up to about 15 wt%. The polymeric coatings doped with the synthesized microspheres can adapt immediately to the varied variation in pH value from the electrochemical corrosion reaction and release active molecules on demand onto the damaged cracks of the coatings on metal surfaces. It leads simultaneously to the dual functions of self‐healing and self‐reporting. The corrosion area can be self‐reported in 6 h, while the substrate can be protected at least for 1 month in 3.5 wt% NaCl solution. These pH‐responsive materials with self‐reporting and self‐healing dual functions are highly expected to have a bright future due to their smart, long‐lasting, recyclable, and multifunctional properties.     

Ceramic tubular MOF hybrid membrane fabricated through in situ layer‐by‐layer self‐assembly for nanofiltration

Nanofiltration has been playing an important role in water purification, in which the developments of novel membrane materials and modules are among significant. Herein, a metal‐organic framework (MOFs) hybrid membrane, ZIF‐8/PSS was fabricated on a tubular alumina substrate through a layer‐by‐layer self‐assembly technique. ZIF‐8 particles in situ grow into PSS layers to improve their compatibility and dispersion, thereby getting high quality membrane, which was loaded into a steel tubular module for nano‐filtrating dyes from water. Under optimized conditions, it shows outstanding nanofiltration properties toward methyl blue, with the flux of 210 Lm^?2 h^?1 MPa^?1 and the rejection of 98.6%. Furthermore, the good pressure resistance ability and running stability of the membrane were revealed, which can be attributed to use the ceramic substrate and the inherent stability of ZIF‐8. This work thus illustrates a simple approach for fabricating MOFs hybrid membranes on tubular ceramic substrates, having great potential for industrial applications. © 2015 American Institute of Chemical Engineers AIChE J, 62: 538–546, 2016     

Self‐healing polymeric materials towards non‐structural recovery of functional properties

Self‐healing of polymers and polymer composites initially represented a process capable of autonomic restoration of mechanical strength upon cracking of the materials, but it is moving into the area of restoration of functionality. This mini‐review is focused on recent efforts to develop functional polymers with built‐in stimuli‐responsive ability to heal for recovery of their specific physical or chemical properties. Molecular design and synthesis, compounding and assembly of organic and inorganic species, inherent reversibility, etc., are summarized. It is hoped that much more interest will be aroused in this emerging and promising frontier topic. © 2014 Society of Chemical Industry     

A seawater‐assisted self‐healing metal–catechol polyurethane with tunable mechanical properties

Recently, self‐healing polymers have been one of the most intriguing academic fields due to the fact that they can increase their service lives and reduce the amount of waste. Here we designed and synthesized a novel telechelic polyurethane with dopamine (DA) end groups that are coordinated with Ca²⁺ to form dynamic non‐covalent bonds. The tensile stress of the designed polyurethanes increases with increase in the amount of metal cation added, while the strain at break slightly decreases. Rheological tests show that the ionic coordination between Ca²⁺ and catechol can dynamically break and recombine under the stimulation of seawater, endowing the polymer with superior self‐healing properties (up to 84% based on toughness). Therefore, the seawater‐triggered self‐healable, super tough polyurethane presented here is very intriguing as it has many potential applications especially in the marine environment. © 2019 Society of Chemical Industry     

A Facile Strategy for Preparing Tough,Self‐Healing Double‐Network Hyaluronic Acid Hydrogels Inspired by Mussel Cuticles

Compared with hydrogel‐like biological tissues such as cartilage, muscles, and blood vessels, current hyaluronic acid hydrogels often suffer from poor toughness and limited self‐healing properties. Herein, a facile and generalizable strategy inspired by mussel cuticles is presented to fabricate tough and self‐healing double‐network hyaluronic acid hydrogels. These hydrogels are composed of ductile, reversible Fe³⁺‐catechol interaction primary networks, and secondarily formed brittle, irreversible covalent networks. Based on this design strategy, the hyaluronic acid hydrogels are demonstrated to exhibit reinforced mechanical strength while maintaining a rapid self‐healing property. In addition, by simply regulating pH or UV irradiation time, the mechanical properties of the hydrogels can be regulated conveniently through variations between the primary and secondary networks.