Investigation of Laser-Induced Graphene (LIG) on a Flexible Substrate and Its Functionalization by Metal Doping for Gas-Sensing Applications.

Graphene materials synthesized using direct laser writing (laser-induced graphene; LIG) make favorable sensor materials because of their large surface area, ease of fabrication, and cost-effectiveness. In particular, LIG decorated with metal nanoparticles (NPs) has been used in various sensors, including chemical sensors and electronic and electrochemical biosensors. However, the effect of metal decoration on LIG sensors remains controversial; hypotheses based on computational simulations do not always match the experimental results, and even the experimental results reported by different researchers have not been consistent. In the present study, we explored the effects of metal decorations on LIG gas sensors, with NO2 and NH3 gases as the representative oxidizing and reducing agents, respectively. To eliminate the unwanted side effects arising from metal salt residues, metal NPs were directly deposited via vacuum evaporation. Although the gas sensitivities of the sensors deteriorate upon metal decoration irrespective of the metal work function, in the case of NO2 gas, they improve upon metal decoration in the case of NH3 exposure. A careful investigation of the chemical structure and morphology of the metal NPs in the LIG sensors shows that the spontaneous oxidation of metal NPs with a low work function changes the behavior of the LIG gas sensors and that the sensors' behaviors under NO2 and NH3 gases follow different principles.

Elastomeric electrolytes for high-energy solid-state lithium batteries.

The use of lithium metal anodes in solid-state batteries has emerged as one of the most promising technologies for replacing conventional lithium-ion batteries1,2. Solid-state electrolytes are a key enabling technology for the safe operation of lithium metal batteries as they suppress the uncontrolled growth of lithium dendrites. However, the mechanical properties and electrochemical performance of current solid-state electrolytes do not meet the requirements for practical applications of lithium metal batteries. Here we report a class of elastomeric solid-state electrolytes with a three-dimensional interconnected plastic crystal phase. The elastomeric electrolytes show a combination of mechanical robustness, high ionic conductivity, low interfacial resistance and high lithium-ion transference number. The in situ-formed elastomer electrolyte on copper foils accommodates volume changes for prolonged lithium plating and stripping processes with a Coulombic efficiency of 100.0 per cent. Moreover, the elastomer electrolytes enable stable operation of the full cells under constrained conditions of a limited lithium source, a thin electrolyte and a high-loading LiNi0.83Mn0.06Co0.11O2 cathode at a high voltage of 4.5 volts at ambient temperature, delivering a high specific energy exceeding 410 watt-hours per kilogram of electrode plus electrolyte. The elastomeric electrolyte system presents a powerful strategy for enabling stable operation of high-energy, solid-state lithium batteries.

Photothermochemical Nanoassembly of 3D Porous Graphene and Palladium Nanoparticles for High-Performance Hydrogen Detection.

Hybrid materials comprising graphene and palladium nanoparticles (PdNPs) are desirable for high-performance hydrogen detection because of the high specific surface area, electron mobility, and flexibility of graphene and the high electrochemical responsivity and reversibility of PdNPs. However, obtaining hybrid materials is energy-intensive and time-consuming. Here, a facile and rapid laser photothermochemical single-step processing method to synchronously produce a nanoassembly of three-dimensional porous graphene and PdNPs from polymer films is reported. Polymers with intrinsic microporosity show high solubility in volatile solvents and miscibility with inorganic materials, allowing the fabrication of homogeneous polymer films containing Pd ligands. The films are photothermally processed using a laser to generate a nanohybrid via photoinduced thermal and chemical processes. The nanohybrid exhibits four-times-enhanced electrical conductivity compared to plain porous graphene, high crystallinity, and coherent covalent metal bonds with a homogeneous size and distribution of PdNPs in hierarchical micro/meso/macroporous graphene structures, allowing high-performance hydrogen sensing (1 ppm) with outstanding mechanical reliability, flexibility, and durability upon bending and twisting. The nanoassembly is integrated with a wireless sensing platform, and hydrogen leakage (1 ppm) is detected using a smart phone. This laser-based nanomanufacturing of the nanoassembly can potentially be applied to wearable detector production platforms in the military and industry.

Synergistic Effects of Various Ceramic Fillers on Thermally Conductive Polyimide Composite Films and Their Model Predictions.

In this study, thermally conductive composite films were fabricated using an anisotropic boron nitride (BN) and hybrid filler system mixed with spherical aluminum nitride (AlN) or aluminum oxide (Al2O3) particles in a polyimide matrix. The hybrid system yielded a decrease in the through-plane thermal conductivity, however an increase in the in-plane thermal conductivity of the BN composite, resulting from the horizontal alignment and anisotropy of BN. The behavior of the in-plane thermal conductivity was theoretically treated using the Lewis⁻Nielsen and modified Lewis⁻Nielsen theoretical prediction models. A single-filler system using BN exhibited a relatively good fit with the theoretical model. Moreover, a hybrid system was developed based on two-population approaches, the additive and multiplicative. This development represented the first ever implementation of two different ceramic conducting fillers. The multiplicative-approach model yielded overestimated thermal conductivity values, whereas the additive approach exhibited better agreement for the prediction of the thermal conductivity of a binary-filler system.

Tailoring biomimetic polymer networks towards an unprecedented combination of versatile mechanical characteristics.

Biomimetic polymeric materials, adopting the basic molecular design principles of biological materials, have been extensively studied in recent years but it is still challenging to combine assorted mechanical characteristics in a single material. Here, we present a simple and effective strategy to prepare mechanically robust yet resilient biomimetic polymer networks by utilizing dual noncovalent and covalent cross-linkings. Tailoring the dual cross-links consisting of thiourea noncovalent interactions and epoxy-amine covalent linkages in the biomimetic polymer networks enables a rare combination of excellent elastic modulus (1.1 GPa), yield stress (39 MPa), extensibility (320%), as well as complete strain and performance recovery after deformation at room temperature. The biomimetic polymer networks also exhibit highly adaptive mechanical properties in response to multiple-stimuli including strain rate, temperature, light, and solvent.

Synthesis of Poly(phenylene polysulfide) Networks from Elemental Sulfur and p-Diiodobenzene for Stretchable, Healable, and Reprocessable Infrared Optical Applications.

The synthesis and characterization of poly(phenylene polysulfide) networks (PSNs) with controlled average sulfur ranks, from elemental sulfur (ES) and p-diiodobenzene (DIB), are investigated. The PSN films, prepared via simple hot pressing, are found to possess large extensibility up to around 300% and complete recovery of shape and mechanical properties after deformation, which are attributed to the loosely cross-linked network structures mainly consisting of linear poly(phenylene polysulfide) chains. The covalent polysulfide linkages in the PSNs also exhibit dynamic behaviors under ultraviolet (UV) or thermal treatment, thus, enabling self-healing and reprocessing of the films when scratched and broken, respectively. Combined with the unique mechanical properties of the PSNs, their high refractive index and excellent infrared (IR) transparency contribute to the preparation of stretchable, healable, and reprocessable IR transmitting materials for potential deformable and stretchable optical applications.

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.

In Situ Polymerization of Dopamine on Graphene Framework for Charge Storage Applications.

Polydopamine, a functional coating material, is redox active as cathode materials for both Li- and Na-ion batteries or hybrid capacitors. Here, a polydopamine coating onto 3D graphene framework is introduced through a simple hydrothermal process, during which graphene oxide serves not only as an oxidant for assisting the polymerization of dopamine, but also as a template for the conformal growth of polydopamine. High-density films are fabricated by compressing the polydopamine-coated graphene aerogels, which can be directly used as free-standing and flexible cathodes in both Li- and Na-cells. The compact electrodes deliver high capacities of ≈230 mAh g-1 in Li-cells and ≈211 mAh g-1 in Na-cells based on the total mass of electrodes. These compact electrodes also exhibit exceptional cycling stability and high rate performance due to the unique structure in which polydopamine is uniformly coated on the 3D structured graphene.

Highly anisotropic thermal conductivity of discotic nematic liquid crystalline films with homeotropic alignment.

Discotic nematic liquid crystal (DNLC) films are prepared by thermal treatment and a photo-crosslinking reaction inside sandwiched glass plates. The DNLC films exhibit outstanding in-plane thermal conductivity which is much larger than cross-plane thermal conductivity. The homeotropic alignment and higher crosslinking density of DNLCs in the films further increase the thermal conductivity anisotropy.

Ultra-hydrophobic sticky polymer surfaces formed by water-induced surface deformation.

Surface properties of poly(oxyethylene)s with alkyl thioether side chains (CH3-nTE; n=carbon atoms in the side chain) were investigated. CH3-nTEs having shorter side chains (n=6, 8, 10) did not have ordered structures, while those with longer chains (n=12, 14) showed well-ordered, lamellar structures with side chain crystalline domains. Accordingly, CH3-12TE and CH3-14TE film surfaces were much more enriched with hydrophobic alkyl side chains than CH3-8TE and CH3-10TE surfaces. However, CH3-12TE and CH3-14TE films had smaller water contact angles (≈114°) than CH3-8TE and CH3-10TE films (>130°). This unexpected behavior is ascribed to the formation of very rough CH3-8TE and CH3-10TE film surfaces (Rrms>100nm) on contact with water. The CH3-10TE/poly(methyl methacrylate) (PMMA) surfaces also showed high water contact angles (>125°), even with low CH3-10TE content (30wt%), because the CH3-10TE moiety roughened the surfaces. Furthermore, ultra-hydrophobic sticky behavior was observed for CH3-nTEs (n=8, 10) and CH3-10TE/PMMA surfaces.

A Carbonaceous Membrane based on a Polymer of Intrinsic Microporosity (PIM-1) for Water Treatment.

As insufficient access to clean water is expected to become worse in the near future, water purification is becoming increasingly important. Membrane filtration is the most promising technologies to produce clean water from contaminated water. Although there have been many studies to prepare highly water-permeable carbon-based membranes by utilizing frictionless water flow inside the carbonaceous pores, the carbon-based membranes still suffer from several issues, such as high cost and complicated fabrication as well as relatively low salt rejection. Here, we report for the first time the use of microporous carbonaceous membranes via controlled carbonization of polymer membranes with uniform microporosity for high-flux nanofiltration. Further enhancement of membrane performance is observed by O2 plasma treatment. The optimized membrane exhibits high water flux (13.30 LMH Bar-1) and good MgSO4 rejection (77.38%) as well as antifouling properties. This study provides insight into the design of microporous carbonaceous membranes for water purification.

Thermally conductive polyamide 6/carbon filler composites based on a hybrid filler system.

We explored the use of a hybrid filler consisting of graphite nanoplatelets (GNPs) and single walled carbon nanotubes (SWCNTs) in a polyamide 6 (PA 6) matrix. The composites containing PA 6, powdered GNP, and SWCNT were melt-processed and the effect of filler content in the single filler and hybrid filler systems on the thermal conductivity of the composites was examined. The thermal diffusivities of the composites were measured by the standard laser flash method. Composites containing the hybrid filler system showed enhanced thermal conductivity with values as high as 8.8 W (m · K)-1, which is a 35-fold increase compared to the thermal conductivity of pure PA 6. Thermographic images of heat conduction and heat release behaviors were consistent with the thermal conductivity results, and showed rapid temperature jumps and drops, respectively, for the composites. A composite model based on the Lewis-Nielsen theory was developed to treat GNP and SWCNT as two separate types of fillers. Two approaches, the additive and multiplicative approaches, give rather good quantitative agreement between the predicted values of thermal conductivity and those measured experimentally.

Thermal conductivity improvement of surface-enhanced polyetherimide (PEI) composites using polyimide-coated h-BN particles.

In this study, we investigated the thermal conductivities and mechanical properties of polyetherimide (PEI) composites using polyimide (PI)-coated h-BN (PI-BN) particles. We found that PI-coated h-BN effectively increased adhesion with the PEI matrix, imparting enhanced mechanical and thermal stability and thermal conductivity with increasing BN content. The thermal conductivity of the PEI composite containing 60 wt% PI-BN was 3.3 W m(-1) K(-1), while the thermal conductivity of the PEI/BN composite without modification was 2.6 W m(-1) K(-1). The PEI/PI-BN composites show higher impact strengths than the PEI/BN composites because of less BN particle agglomeration and good wettability between PEI and h-BN. The results indicate that the PI-coated BN incorporated into the PEI matrix effectively enhances the thermal conductivity and mechanical properties of the PEI composites.

Drawing circuits with carbon nanotubes: scratch-induced graphoepitaxial growth of carbon nanotubes on amorphous silicon oxide substrates.

Controlling the orientations of nanomaterials on arbitrary substrates is crucial for the development of practical applications based on such materials. The aligned epitaxial growth of single-walled carbon nanotubes (SWNTs) on specific crystallographic planes in single crystalline sapphire or quartz has been demonstrated; however, these substrates are unsuitable for large scale electronic device applications and tend to be quite expensive. Here, we report a scalable method based on graphoepitaxy for the aligned growth of SWNTs on conventional SiO2/Si substrates. The "scratches" generated by polishing were found to feature altered atomic organizations that are similar to the atomic alignments found in vicinal crystalline substrates. The linear and circular scratch lines could promote the oriented growth of SWNTs through the chemical interactions between the C atoms in SWNT and the Si adatoms in the scratches. The method presented has the potential to be used to prepare complex geometrical patterns of SWNTs by 'drawing' circuits using SWNTs without the need for state-of-the-art equipment or complicated lithographic processes.

One-step synthesis of carbon nanosheets converted from a polycyclic compound and their direct use as transparent electrodes of ITO-free organic solar cells.

Through a catalyst- and transfer-free process, we fabricated indium tin oxide (ITO)-free organic solar cells (OSCs) using a carbon nanosheet (CNS) with properties similar to graphene. The morphological and electrical properties of the CNS derived from a polymer of intrinsic microporosity-1 (PIM-1), which is mainly composed of several aromatic hydrocarbons and cycloalkanes, can be easily controlled by adjusting the polymer concentration. The CNSs, which are prepared by simple spin-coating and heat-treatment on a quartz substrate, are directly used as the electrodes of ITO-free OSCs, showing a high efficiency of approximately 1.922% under 100 mW cm(-2) illumination and air mass 1.5 G conditions. This catalyst- and transfer-free approach is highly desirable for electrodes in organic electronics.

Silver-perfluorodecanethiolate complexes having superhydrophobic, antifouling, antibacterial properties.

Silver-perfluorodecanethiolate complexes having superhydrophobic, antifouling, antibacterial properties were prepared by a reaction of silver nitrate with perfluorodecanethiol. When the silver nitrate to perfluorodecanethiol molar ratio was 1/2, silver-perfluorodecanethiolate complexes having hierarchical micro-/nano-sized wire shapes were obtained, and they showed superhydrophobic and antifouling properties. After UV irradiation, silver nanoparticles were generated on the wires and exhibited antibacterial properties.

Effect of n-alkyl and sulfonyl groups on the wetting properties of comblike poly(oxyethylene)s and stick-slip behavior.

The influence of side chain length and sulfonyl moiety on the molecular structures and wettability behavior of poly(oxyethylene)s with alkyl sulfonyl side chains (CH(3)-nSE, n = 1, 2, 3, 4, 5, 6, 8, 10), where n is the number of the carbon atom in the n-alkyl side group, was investigated. CH(3)-nSEs having shorter side chains (n < 5) do not have ordered structures, and their surfaces were found to be more polar than those of CH(3)-nSEs having longer side chains (n ≥ 5). The CH(3)-nSEs having longer side chains show double-layered lamellar structures (n ≥ 5) with well-aligned side chains and low surface energies in the range 21.2-25.8 mN/m. Interestingly, stick-slip behavior was observed only on the surfaces of CH(3)-3SE and CH(3)-4SE when water was used as the test liquid. The surface deformation at the three-phase line was generated from interactions between water and sulfonyl groups, and the optimum side chain lengths were believed to cause the stick-slip behavior.

Wettability of the morphologically and compositionally varied surfaces prepared from blends of well ordered comb-like polymer and polystyrene.

Phase-separated surfaces of blends of polystyrene (PS) and well ordered comb-like polymer, poly[(oxy(decylsulfonylmethyl)ethylene)] (CH(3)-10SE), were prepared by spin casting polymer mixtures. Various surface morphologies, such as holes, islands, connected islands and pillars, were prepared by changing the blend compositions. Due to the influence of the CH(3)-10SE domain with a well ordered molecular conformation, a very low energy surface (≈22mN/m) was created, which is close to the value of the pure polymer (≈20mN/m), even when the blends contained only 20wt.% of the pure polymer. Furthermore, by selective etching the PS domain in the blend surfaces, the advancing contact angles of water and n-hexadecane were highly increased from 113.5° and 43.2° for the pure CH(3)-10SE surface to 133.3° and 67.2° for the CH(3)-10SE structural surfaces with holes prepared using the solvent etching method, respectively. The result of the water advancing contact angles measured on the samples immersed in water over 20days showed that the film stability of CH(3)-10SE could be improved considerably by even adding small amounts of PS.

Inhibition of bacterial adhesion on well ordered comb-like polymer surfaces.

The surfaces of comb-like poly(oxyethylene) derivatives with n-alkylsulfonyl side groups were more effective at reducing Pseudomonas aeruginosa adhesion than the surfaces of common materials such as polystyrene, poly(methyl methacrylate), poly(dimethylsiloxane), fluorinated polyacrylate, and glass. When the comb-like poly(oxyethylene) was mixed with polystyrene and poly(methyl methacrylate), the topology and roughness of the surfaces varied according to the mixture compositions. However the surface energies of the mixtures were close to that of the comb-like poly(oxyethylene) in the range of 21-23 mN/m and bacterial adhesion resistances of the mixture surfaces were also comparable to that of the pure comb-like poly(oxyethylene) surface.