Influence of Thiol-Functionalized Polysilsesquioxane/Phosphorus Flame-Retardant Blends on the Flammability and Thermal, Mechanical, and Volatile Organic Compound (VOC) Emission Properties of Epoxy Resins.

In this study, thiol-functionalized ladder-like polysesquioxanes end-capped with methyl and phenyl groups were synthesized via a simple sol-gel method and characterized through gel permeation chromatography (GPC), Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR), and thermogravimetric analysis (TGA). Additionally, epoxy blends of different formulations were prepared. Their structural, flame-retardant, thermal, and mechanical properties, as well as volatile organic compound (VOC) emissions, were determined using differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), TGA, scanning electron microscopy (SEM), limiting oxygen index (LOI), cone calorimetry, and a VOC analyzer. Compared to epoxy blends with flame retardants containing elemental phosphorus alone, those with flame retardants containing elemental phosphorus combined with silicon and sulfur exhibited superior thermal, flame-retardant, and mechanical properties with low VOC emissions. SEM of the residual char revealed a dense and continuous morphology without holes or cracks. In particular, LOI values for the combustion of methyl and phenyl end-capped polysilsesquioxane mixtures were 32.3 and 33.7, respectively, compared to 28.4% of the LOI value for the blends containing only phosphorus compounds. The silicon-sulfur-phosphorus-containing blends displayed reduced flammability concerning the blends using a flame retardant containing only phosphorus. This reflects the cooperative effects of various flame-retardant moieties.

Nano-emulsification of oriental lacquer sap by ultrasonic wave propagation: Improvement of thin-film characteristics as a natural resin.

Lacquer sap has received much attention as a traditional natural resin because it is a renewable and eco-friendly biopolymer resource unlike artificial coating materials. However, strict drying conditions and long drying times of lacquer sap should be modified to expand its applications. This study presents the first attempt to investigate the effect of different amplitudes of ultrasonic waves on the lacquer sap composed of water-in-oil (W/O) emulsion droplets and the mechanical properties of the resultant film by solvent evaporation. Acoustically induced cavitation via batch ultrasonication facilitates the generation of submicron-sized W/O emulsion. The drying time of sonicated lacquer sap was noticeably shortened as the amplitude of acoustic power increased. Interestingly, the transparency of the film cast from lacquer sap consisting of the smallest emulsion droplets increased significantly, weakening the degree of colour change from caramel-like yellow to dark brown as polymerisation progressed. These are attributed to the effective and frequent contact of laccase enzyme with urushiol at the increased interfacial area of nano-emulsified W/O droplets pulverised by ultrasonic waves. The quinone radical-generation in the interface layer and its transfer to the urushiol oil phase through water-insoluble glycoprotein emulsifier are greatly promoted, resulting in highly cross-linked, dense three-dimensional polymer networks, which also increased the lacquer film hardness after drying. As the emulsion droplet size decreased, the mutual interaction between the catechol moiety of urushiol and the substrates increased, resulting in improved adhesion. The nano-emulsification of the lacquer sap by ultrasonic waves can be used in a simple, effective, and eco-friendly way to shorten the drying time and improve the film characteristics of natural resins. This approach could pave the way for its wide range of applications in industrial fields, taking into account green and sustainable chemistry.

Chemical and geometrical criteria for the release of elastomeric 1D nanoarrays from porous nanotemplates.

Releasing 1D nanoarrays from nanotemplates is a significant challenge for the integration of mechanically soft materials in a variety of newly emerging technological areas. To fabricate nanoarrays without defects, the combined effects of the surface energy and the geometric features of the nanotemplate should be considered. A previously reported approach based on the correlation between the adhesion energy and the real contact area was not satisfactory to describe the rupture conditions of the nanofibers while they were being peeled off from the porous template. Here we demonstrate that the aspect ratio rather than the contact area of the nanoporous template is the key factor determining the upper limit of the pore length of the nanotemplate with respect to the rupture of the nanoarray during separation. We propose that the value of alpha(c)*, which is calculated with a simple expression in which the adhesion energy is multiplied by the aspect ratio, can be used as an excellent criterion for the fabrication of 1D nanoarrays without defects with a simple peel-off processes. Our approach opens up new applications for unconventional lithographic techniques, such as soft lithography, imprint lithography, and others.

Superamphiphilic Janus fabric.

Janus fabrics with superamphiphilicity were fabricated via electrospinning of polyacrylonitrile (PAN). PAN nanofibrous mats were formed on an aluminum foil substrate and then thermally treated to cause hydrolysis. An identical PAN solution was subsequently electrospun onto the hydrolyzed PAN layer, followed by peeling off of the bicomposite film from the collector substrate to produce a free-standing Janus fabric. On one side, the electrospun PAN mat exhibited superhydrophobic properties, with a water contact angle of 151.2°, whereas the initially superhydrophobic PAN sheet on the opposite side of the fabric was converted to a superhydrophilic surface (water contact angle of 0°) through hydrolysis of the surface functional groups induced by the thermal treatment. The resulting Janus fabrics exhibited both superhydrophobicity, repelling water on the one side, and superhydrophilicity, absorbing water on the other side. The organic solvent resistance of the PAN nanofibrous sheets was remarkably improved by incorporation of a tetraethyl orthosilicate. This facile and simple technique introduces a new route for the design and development of functional smart, robust fabrics from an inexpensive, commercially available polymer.

pH-Induced antireflection coatings derived from hydrogen-bonding-directed multilayer films.

Hydrogen-bonding-directed layer-by-layer assembled films, based on polystyrene-block-poly(acrylic acid) (PS-b-PAA) block copolymer micelles and poly(4-vinylpyridine) (P4VP), were successfully fabricated in methanol. Varying the PAA content in the PS-b-PAA micelles afforded control over the film growth properties, especially the multilayer film thickness. Interestingly, antireflection films with refractive indices that could be tuned between 1.58 and 1.28 were obtained by treatment with an aqueous HCl solution (pH 2.27), and the transmittance obtained was as high as 98.4%. In acid solution, the pyridine group was protonated, destroying the hydrogen bonding between P4VP and PAA. A concomitant pH-induced polymer reorganization in the multilayers resulted in a porous honeycomb-like texture on the substrate.

Actively Operable Thermoresponsive Smart Windows for Reducing Energy Consumption.

Efficient usage of finite energy resources is a core approach for preventing major blackouts caused by a severe lack of energy. Smart windows, which modulate thermal energy transferred from the incident sunlight, have attracted tremendous interest as an alternative technology for resolving the fast-approaching energy crisis by suppressing unnecessary energy usage such as air conditioning or heating inside buildings. Here, we demonstrate a set of materials and design concepts for doubly responsive smart windows, which efficiently reduce the consumption of our limited energy reserves. The proposed smart windows are based on the concept of combining the lower critical solution temperature of thermoresponsive polymer hydrogels and the electrical actuation of graphene-based flexible heaters; this combination serves to actively control the passive-type moving thermoresponsive smart window. The proposed smart windows exhibit a highly tunable transparency of above 90%, which corresponds to an almost instantaneous change from high transmission of the incident light to the complete blockage of its penetration under thermal or electrical stimulation. In particular, when the windows of a mockup house are replaced with the developed flexible smart windows, the increment rate of the indoor temperature under white light irradiation reduces drastically. This type of active light control system is expected to create a new opportunity for achieving cost savings on heating, cooling, and lighting through management of light energy transmitted into the interior of a house.

Ecofriendly Catechol Lipid Bioresin for Low-Temperature Processed Electrode Patterns with Strong Durability.

We demonstrated catechol lipid-based bioresin, which is collected from lacquer trees, to produce conductive pastes that can be processed at low temperatures, which are highly adhesive and multidurable. Our conductive paste, which consists of catechol lipid-based urushiol resin and a multimodal mixture of silver fillers, exhibited stable dispersion with shear thinning properties. The urushiol lacquer induced spontaneous reduction of silver salt at the surface of the silver fillers, thereby contributing to lower the contact resistance between conductive fillers in the electrical conduction. Furthermore, the directional volume shrinkage of the urushiol lacquer matrix in a cross-linking reaction resulted in a highly ordered microstructure of the silver fillers with layer-by-layer stacking of the silver flakes. This structure contributed to the improvement of the electrical contact between fillers as well as excellent mechanical hardness, anti-scratch capability, and the long-term environmental stability of the conductive films. Conductive films based on the silver paste with urushiol lacquer exhibited low electrical resistivity below 4.4 × 10-5 Ω cm, 5B-class strong adhesion strength, and high hardness exceeding 200 MPa. Finally, we demonstrated the facile room-temperature processability and screen printability of the UL-Ag paste by fabricating a printed antenna and three-dimensional (3D) electrode assembly based on a plastic 3D block.

Anisotropy-Driven High Thermal Conductivity in Stretchable Poly(vinyl alcohol)/Hexagonal Boron Nitride Nanohybrid Films.

Controlling the anisotropy of two-dimensional materials with orientation-dependent heat transfer characteristics is a possible solution to resolve severe thermal issues in future electronic devices. We demonstrate a dramatic enhancement in the in-plane thermal conductivity of stretchable poly(vinyl alcohol) (PVA) nanohybrid films containing small amounts (below 10 wt %) of hexagonal boron nitride ( h-BN) nanoplatelets. The h-BN nanoplatelets were homogeneously dispersed in the PVA polymer solution by ultrasonication without additional surface modification. The mixture was used to prepare thermally conductive nanocomposite films. The in-plane thermal conductivity of the resulting PVA/ h-BN nanocomposite films increased to 6.4 W/mK when the strain was increased from 0 to 100% in the horizontal direction. More specifically, the thermal conductivity of a PVA/ h-BN composite film with 10 wt % filler loading can be improved by up to 32 times as compared to pristine PVA. This outstanding thermal conductivity value is significantly larger than that of materials currently used in in-plane thermal management systems. This result is attributed to the anisotropic alignment of h-BN particles in the PVA chain matrix during stretching, enhancing phonon conductive paths and hence improving the thermal conductivity and thermal properties of PVA/ h-BN nanocomposite films. These polymer nanocomposites have low cost as the amount of expensive conductive fillers is reduced and can be potentially used as high-performance materials for thermal management systems such as heat sink and thermal interface materials, for future electronic and electrical devices.

Roll-to-roll redox-welding and embedding for silver nanowire network electrodes.

We developed a continuous roll-to-roll redox-welding and embedding method for the fabrication of electrodes of silver nanowire (AgNWs) networks. The roll-to-roll welding method involved a sequence of oxidation and reduction reactions in an aqueous solution. The redox-welding significantly decreased the sheet resistance of the AgNW film owing to the strong fusion and interlocking at the nanowire junction, while the optical transmittance was maintained. The first oxidation step using HNO3 generated ionized silver (Ag+) which got re-deposited onto the nanowire junctions via an autocatalytic reaction. The oxide layers, which formed on the nanowire surface by both air exposure and the first step of oxidation, were removed by the second reduction step using NaBH4. The redox-welded AgNW electrodes exhibited a sheet resistance of 11.3 Ω sq-1 at the optical transmittance of 90.5% at 550 nm. Furthermore, redox-welding of the AgNWs significantly enhanced their mechanical robustness compared to that of the as-coated AgNWs. The redox-welded AgNWs embedded in a UV curable resin, using a roll-to-roll embedding process, were successfully applied as anode electrodes for large-area and flexible organic light emitting diodes (OLEDs). The device performance is superior to that of a device based on the as-coated AgNW electrode, and is also comparable to that of a device using commercial ITO as the electrode. The redox-welding and embedding processes provide a facile and reliable method for fabricating large-area transparent flexible electrodes for next-generation flexible optoelectronic devices.

Instantaneous Pulsed-Light Cross-Linking of a Polymer Gate Dielectric for Flexible Organic Thin-Film Transistors.

We report the instantaneous pulsed-light cross-linking of polymer gate dielectrics on a flexible substrate by using intensely pulsed white light (IPWL) irradiation. Irradiation with IPWL for only 1.8 s of a poly(4-vinylphenol) (PVP) thin film with the cross-linking agent poly(melamine-co-formaldehyde) (PMF) deposited on a plastic substrate was found to yield fully cross-linked PVP films. It was confirmed that the IPWL-cross-linked PVP films have smooth pinhole-free surfaces and exhibit a low leakage current density, organic solvent resistance, and good compatibility with organic semiconductor, and that they can be used as replacements for typical PVP dielectrics that are cross-linked with time and energy intensive thermal heating processes. The synchronization of the IPWL irradiation with substrate transfer was found to enable the preparation of cross-linked PVP films on large area substrates with a highly uniform capacitance. Flexible OTFT based on IPWL-cross-linked PVP dielectrics were found to exhibit good electrical performance that is comparable to that of devices with thermally cross-linked PVP dielectric, as well as excellent deformation stability even at a bending radius of 3 mm.

Centro-Apical Self-Organization of Organic Semiconductors in a Line-Printed Organic Semiconductor: Polymer Blend for One-Step Printing Fabrication of Organic Field-Effect Transistors.

Here we report the first demonstration for centro-apical self-organization of organic semiconductors in a line-printed organic semiconductor: polymer blend. Key feature of this work is that organic semiconductor molecules were vertically segregated on top of the polymer phase and simultaneously crystallized at the center of the printed line pattern after solvent evaporation without an additive process. The thickness and width of the centro-apically segregated organic semiconductor crystalline stripe in the printed blend pattern were controlled by varying the relative content of the organic semiconductors, printing speed, and solution concentrations. The centro-apical self-organization of organic semiconductor molecules in a printed polymer blend may be attributed to the combination of an energetically favorable vertical phase-separation and hydrodynamic fluids inside the droplet during solvent evaporation. Finally, a centro-apically phase-separated bilayer structure of organic semiconductor: polymer blend was successfully demonstrated as a facile method to form the semiconductor and dielectric layer for OFETs in one- step.

Graphene oxide nanosheet wrapped white-emissive conjugated polymer nanoparticles.

We have demonstrated the preparation of white-emissive conjugated polymer nanoparticles wrapped with graphene oxide (GO) nanosheets. Highly stable, GO-wrapped, poly(9,9-di-n-octylfluorenyl-2,7-diyl) nanoparticles (GO-PFO NPs) with diameters in the range 30-150 nm were successfully obtained by utilizing the GO nanosheets as an interface stabilizer in an emulsification process. The synthesized GO-PFO NPs exhibited unique white-emitting photoluminescence with a characteristic green-emissive broad band above 500 nm, which was distinct from the photoluminescent behavior of PFO NPs without GO. This green emission was deduced to originate from the presence of the GO nanosheet shell surrounding the PFO NPs, rather than from luminescence of GO itself or formation of keto defects in the PFO chain. PL decay analysis showed that the GO-wrapped PFO NPs had a longer luminescence lifetime in comparison to PFO NPs without GO, and highly efficient energy transfer to lower energy state induced by the GO occurred.

Polyelectrolyte interlayer for ultra-sensitive organic transistor humidity sensors.

We demonstrate low-voltage, flexible, transparent pentacene humidity sensors with ultrahigh sensitivity, good reliability, and fast response/recovery behavior. The excellent performances of these devices are derived from an inserted polyelectrolyte (poly[2-(methacryloyloxy)ethyltrimethylammonium chloride-co-3-(trimethoxysilyl)propyl methacrylate] (poly(METAC-co-TSPM)) interlayer, which releases free Cl- ions in the electrolyte dielectric layer under humid conditions and boosts the electrical current in the transistor channel. This has led to extreme device sensitivity, such that electrical signal variations exceeding 7 orders of magnitude have been achieved in response to a 15% change in the relative humidity level. The new sensors exhibit a fast responsivity and a stable performance toward changes in humidity levels. Furthermore, the humidity sensors, mounted on flexible substrates, provided low voltage (<5 V) operation while preserving the unique ultrasensitivity and fast responsivity of these devices. We believe that the strategy of utilizing the enhanced ion motion in an inserted polyelectrolyte layer of an OFET structure can potentially improve sensor technologies beyond humidity-responsive systems.

Dynamic swelling of tunable full-color block copolymer photonic gels via counterion exchange.

One-dimensionally periodic block copolymer photonic lamellar gels with full-color tunability as a result of a direct exchange of counteranions were fabricated via a two-step procedure comprising the self-assembly of a hydrophobic block-hydrophilic polyelectrolyte block copolymer, polystyrene-b-poly(2-vinyl pyridine) (PS-b-P2VP), followed by sequential quaternization of the P2VP layers in 1-bromoethane solution. Depending on the hydration characteristics of each counteranion, the selective swelling of the block copolymer lamellar structures leads to large tunability of the photonic stop band from blue to red wavelengths. More extensive quaternization of the P2VP block allows the photonic lamellar gels to swell more and red shift to longer wavelength. Here, we investigate the dynamic swelling behavior in the photonic gel films through time-resolved in situ measurement of UV-vis transmission. We model the swelling behavior using the transfer matrix method based on the experimentally observed reflectivity data with substitution of appropriate counterions. These tunable structural color materials may be attractive for numerous applications such as high-contrast displays without using a backlight, color filters, and optical mirrors for flexible lasing.

Counterion-induced reversibly switchable transparency in smart windows.

Smart windows that can reversibly alternate between extreme optical characteristics via clicking counteranions of different hydration energies were developed on glass substrates through the facile spray-casting of poly[2-(methacryloyloxy)ethyltrimethylammonium chloride-co-3-(trimethoxysilyl)propyl methacrylate]. The optical transmittance was either 90.9% or 0% over the whole spectral range when alternately immersed in solutions containing thiocyanate (SCN(-)) or bis(trifluoromethane)sulfonimide (TFSI(-)) ions, respectively. The extreme optical transitions were attributed to formation of microporous structures via the molecular aggregation of polyelectrolyte chains bearing TFSI(-) ions in methanol. Because the smart windows were either highly transparent toward or completely blocking of incident light upon direct counterion exchange, this kind of nanotechnology may provide a new platform for efficiently conserving on energy usage in the interior of buildings.

Effect of nanostructure on the surface dipole moment of photoreversibly tunable superhydrophobic surfaces.

Fluorinated azobenzene-modified nanoporous substrates were fabricated such that the surface properties were photoreversibly converted between superhydrophobicity and superhydrophilicity as a result of UV irradiation. This result was attributed to the enhanced surface roughness of the nanostructured surface, which supplied sufficient free space within the monolayer for the tethered azobenzenes to facilely isomerize.

Nanocarbon-induced rapid transformation of polymer surfaces into superhydrophobic surfaces.

We present a facile method for fabricating superhydrophobic polymer surfaces by solubility modulation and nanocarbon (NC)-induced crystallization of polycarbonate (PC). The method consists of dipping polymer sheets in a solvent in which the polymer is partially soluble and then inducing solution crystallization by dipping the sheet in a poor solvent for several seconds. A solvent mixture of methyl ethyl ketone and isopropyl alcohol (IPA) was optimized to shorten the crystallization time in a poor solvent. Single-walled carbon nanotubes, multiwalled carbon nanotubes (MWNTs), and graphene sheets were used to nucleate PC crystallization. In particular, monolayer graphene sheets were prepared by reducing graphene oxide with hydrazine. Crystalline micro- and nanostructures rapidly formed upon dipping of the PC sheets in the solution containing NCs, followed by immersion in IPA. The structures depended on the dimensions of the NCs. Especially, in the MWNT solution, dipping for 10 s was sufficient to create a superhydrophobic surface. Crystallization of PC and the incorporation of NCs during crystallization were characterized by Raman spectroscopy.

Robust superhydrophobic mats based on electrospun crystalline nanofibers combined with a silane precursor.

We demonstrate the fabrication of solvent-resistant, mechanically robust, superhydrophobic nanofibrous mats by electrospinning of poly(vinylidene fluoride) (PVDF) in the presence of inorganic silane materials. The solvent resistance and mechanical strength of nanofibrous mats were dramatically increased through the crystallization of as-spun PVDF fibers or incorporation of a tetraethyl orthosilicate (TEOS) sol into the nanofibrous matrix. The electrospun nanofibrous mats yielded a water contact angle of 156 degrees that did not vary with TEOS content. The solvent resistance and mechanical robustness of the electrospun mats were significantly enhanced through extensive cross-linking of TEOS, even after short PVDF annealing times. The interpenetrating polymer network, which embeds polymer chains in a TEOS network, allows the fabrication of robust functional nanofibers by combining semicrystalline polymers with electrospinning techniques.

Photoreversibly switchable superhydrophobic surface with erasable and rewritable pattern.

We report the facile fabrication of a functional nanoporous multilayer film with wettability that is reversibly tunable between superhydrophobicity and superhydrophilicity with UV/visible irradiation. Our approach controls surface roughness with an electrostatic self-assembly process and makes use of the photoresponsive molecular switching of fluorinated azobenzene molecules. Selective UV irradiation onto the nanostructured substrate was used to realize substrates with erasable and rewritable patterns of extreme wetting properties. Our findings will open up new avenues for external stimuli-responsive smart surfaces.