Design of a Bioinspired Robust Three-Dimensional Cross-Linked Polymer Binder for High-Performance Li-Ion Battery Applications.

Si has the highest theoretical capacity (4200 mA h g-1) among conventional anode materials, such as graphite (372 mA h g-1), but its large volume expansion leads to deterioration of the battery performance. To overcome this problem (issue), we investigated the use of polysaccharide-based 3D cross-linked network binders for Si anodes, in which the polysaccharide formed an effective 3D cross-linked network around Si particles via cross-linking of polysaccharide with citric acid (CA). Sodium alginate (SA), a natural polysaccharide extracted from brown algae, is a suitable binder material for Si anodes because its abundant hydroxyl (-OH) and carboxyl (-COOH) groups form hydrogen and covalent bonds with the -OH groups present on the Si surface. We found that CA-cross-linked (CA-SA) could effectively prevent the volume expansion of Si anodes through the formation of 3D cross-linked network structures. In addition, the CA-SA binders provide enhanced adhesion strength, enabling the fabrication of more robust electrodes than those prepared using binders with linear structures ("linear binders"). In particular, the fabricated Si-based electrode (high mass loading of 1.5 mg cm-2) with CA-SA binder exhibited outstanding areal capacity (∼2.7 mA h cm-2) and excellent cycle retention (∼100% after 100 cycles).

Passive Daytime Radiative Cooling by Thermoplastic Polyurethane Wrapping Films with Controlled Hierarchical Porous Structures.

Invited for this month's cover is a combined work of the Korea Research Institute of Chemical Technology together with the Chungnam National University, the University of California, Irvine, and Chung-Ang University. The cover shows the effective thermal management of a vehicle interior through the wrapping of stretchable passive radiative cooling film. Thermoplastic polyurethane (TPU) cooler film with a hierarchical porous structure shows a dramatic cooling effect compared to commercial paint in sunny, hot weather. The Research Article itself is available at 10.1002/cssc.202201842.

Passive Daytime Radiative Cooling by Thermoplastic Polyurethane Wrapping Films with Controlled Hierarchical Porous Structures.

Current research has focused on effective solutions to mitigate global warming and the accelerating greenhouse gas emissions. Compared to most cooling methods requiring energy and resources, passive daytime radiative cooling (PDRC) technology offers excellent energy savings as it requires no energy consumption. However, existing PDRC materials encounter unprecedented problems such as complex structures, low flexibility, and performance degradation after stretching. Thus, this study reports a porous structured thermoplastic polyurethane (TPU) film with bimodal pores to produce high-efficiency PDRC with efficient solar scattering using a simple process. The TPU film exhibited an adequately high solar reflectivity of 0.93 and an emissivity of 0.90 in the atmospheric window to achieve an ambient cooling of 5.6 °C at midday under a solar intensity of 800 W m-2 . Thus, the highly elastic and flexible TPU film was extremely suitable for application on objects with complex shapes. The radiative cooling performance of 3D-printed models covered with these TPU films demonstrated their superior indoor cooling efficiency compared to commercial white paint (8.76 °C). Thus, the proposed design of high-efficiency PDRC materials is applicable in various urban infrastructural objects such as buildings and vehicles.

Preparation and Electrochemical Characterization of Si@C Nanoparticles as an Anode Material for Lithium-Ion Batteries via Solvent-Assisted Wet Coating Process.

Silicon-based electrodes are widely recognized as promising anodes for high-energy-density lithium-ion batteries (LIBs). Silicon is a representative anode material for next-generation LIBs due to its advantages of being an abundant resource and having a high theoretical capacity and a low electrochemical reduction potential. However, its huge volume change during the charge-discharge process and low electrical conductivity can be critical problems in its utilization as a practical anode material. In this study, we solved the problem of the large volume expansion of silicon anodes by using the carbon coating method with a low-cost phenolic resin that can be used to obtain high-performance LIBs. The surrounding carbon layers on the silicon surface were well made from a phenolic resin via a solvent-assisted wet coating process followed by carbonization. Consequently, the electrochemical performance of the carbon-coated silicon anode achieved a high specific capacity (3092 mA h g-1) and excellent capacity retention (~100% capacity retention after 50 cycles and even 64% capacity retention after 100 cycles at 0.05 C). This work provides a simple but effective strategy for the improvement of silicon-based anodes for high-performance LIBs.

Photothermal Fabrics for Efficient Oil-Spill Remediation via Solar-Driven Evaporation Combined with Adsorption.

Oil spill rapidly destroys aquatic system and threatens humans, requiring fast and efficient remedy for removal of oil. The conventional remedy employs water-floating oil adsorbents whose volume should be large enough to accommodate all oil ingredients. Here, we suggest a new concept for efficient oil-spill remediation, which combines solar-driven evaporation of light oil components and simultaneous adsorption of heavy oil components, namely, solar-driven evaporation of oil combined with adsorption (SEOA). To design photothermal oil absorbents for the efficient SEOA, we designed carbonaceous fabrics with high photothermal heating performance and oil-adsorption capacity by carbonizing nonwoven cotton fabrics. For three model organic solvents of octane, decane, and dodecane floating on water, the fabrics, respectively, accelerated the evaporation in factors of 2.0, 4.4, and 2.3 through photothermal heating under simulated sunlight condition. For the 1.18 mm thick crude oil floating on water, 70 and 77 wt % of crude oil were evaporated within 2 and 16 h, respectively, with the photothermal fabrics, whereas only 22 and 34 wt % was evaporated in the absence of the fabrics, indicating the dramatic enhancement of oil removal by solar-driven evaporation. The remaining heavy oil components were accommodated in the pores of the fabrics, removal of which showed an additional 18 wt % reduction; that is, a total 95 wt % of the crude oil was removed. The oil-treatment capacity is as high as 110 g g-1, which has never been achieved with conventional oil adsorbents to the best of our knowledge. We believe that our combinatorial SEOA approach potentially contributes to minimizing the environmental disaster through a fast and efficient oil-spill remediation.

Electrically stimulable indium tin oxide plate for long-term in vitro cardiomyocyte culture.

BACKGROUND: We investigated whether electrical stimulation via indium tin oxide (ITO) could enhance the in vitro culture of neonatal rat ventricular myocytes (NRVMs), which are important in vitro models for studying the mechanisms underlying many aspects of cardiology. METHODS: Cardiomyocytes were obtained from 1-day-old neonatal rat heart ventricles. To evaluate function of NRVMs cultured on ITO with electrical stimulation, the cell viability, change of cell morphology, immunochemistry using cardiac-specific antibodies, and gene expression were tested. RESULTS: Defined sarcomeric structure, cell enlargement, and increased distribution of NRVMs appeared in the presence of electrical stimulation. These characteristics were absent in NRVMs cultured under standard culture conditions. In addition, the expression levels of cardiomyocyte-specific and ion channel markers were higher in NRVMs seeded on ITO-coated dishes than in the control group at 14 days after seeding. ITO-coated dishes could effectively provide electrical cues to support the in vitro culture of NRVMs. CONCLUSIONS: These results provide supporting evidence that electrical stimulation via ITO can be effectively used to maintain culture and enhance function of cardiomyocytes in vitro.

Dewetting of Thin Polymer Films on Wrinkled Graphene Oxide Monolayers.

We investigated the effect of the morphological structure of a graphene oxide (GO) monolayer on the dewetting dynamics of the upper polymer thin films. The Langmuir-Schaefer (LS) technique was used to prepare a wrinkled GO ( wrGO) structure with a root mean square (rms) roughness of 22.7 Å. The dewetting behavior of poly(methyl methacrylate) (PMMA) thin films on the wrGO monolayers was perfectly prevented, whereas the PMMA thin films on a flat GO monolayer were dewetted at 203 °C. This wrinkle effect of the GO can be also obtained when the GOs monolayers are intercalated to the PMMA/polystyrene (PS) interface. In this multilayer, the flat GO monolayer at the interface between the PS and PMMA layers was spontaneously roughened with rms roughness of 46.9 Å after annealing and also prohibited the dewetting behavior. From the results, we found that to improve the compatibility of polymer blends by adding the two-dimensional nanosheets, it is important to control the morphological structure of the sheets at the interface, along with manipulation of the GO-polymer interactions.

Fabrication of Wettability-Patterned Surface for Cellular Micropatterning Using Step-Wise Ion Beam Processing.

In this study, the fabrication of a wettability patterned surface for cellular micropatterning was investigated using step-wise ion beam processing. A perfluorinated poly(ethylene-co-propylene) (FEP) film was first irradiated using accelerated Xe+ ions with 100 keV of energy at the low current density of 1 µA/cm² over the entire surface. Second, its confined regions were irradiated at the higher current density of 15 µA/cm² at various ion fluences through the pattern mask to generate patterns with big differences in wettability. From the analytic results, it was clearly verified that the step-wise irradiation induced effective chemical and morphological changes on the FEP surface, resulting in the successful formation of well-defined micropatterns with relatively hydrophilic and superhydrophobic surfaces. Moreover, the results of in-vitro cell culture showed well-resolved formation of 200 µm cell micropatterns on the wettability patterned FEP surface due to the individual effects of the relatively hydrophilic and superhydrophobic properties on the cell adhesiveness and proliferation.

Free-Standing Janus Graphene Oxide with Anisotropic Properties for 2D Materials as Surfactant.

We present a simple and facile approach to creating asymmetrically modified graphene oxide sheets by grafting polymers with different polarities. Single-layered Janus graphene derivatives were prepared by grafting polymers with different polarities at the liquid-gas interface through one step functionalization. This approach allows obtaining free-standing monolayers of Janus graphene oxide sheets for large area, and also controlling the morphology (i.e., wrinkled Janus graphene oxide sheets) by a compression monolayer. A neutron reflectivity technique is used to check the functionalization on each side of the monolayer, and the results are compared with contact angles to determine its amphiphilic nature. The free-standing Janus monolayers become robust after UV-irradiation, and are able to withstand various solvents. Because these robust Janus graphene films can maintain their anisotropic functionalities over time, this technique provides a new strategy for fabricating functional materials that require amphiphilic properties (i.e., oil-water separation membranes and chemical compatibilizers functioning as a 2D surfactant) and different electrical functionalities (i.e., flexible lightweight p-n junction semiconductors and stimuli-driven actuators).

Preparation of Conductive Carbon Films from Novolac Resins by Ion Beam Irradiation and Carbonization.

In this study, thin carbon films with good electrical properties were prepared using commercial novolac resins by ion beam irradiation and carbonization. Novolac films were irradiated with ion beams and then carbonized under inert atmosphere. Based on the FTIR and UV results, the novolac resins were found to be crosslinked by ion beam irradiation without any additives. The Raman and XRD results indicate that carbon films with pseudo-graphitic structures were formed by carbonization of the ion beam irradiated novolac films. The sheet resistance of the prepared carbon films decreased to 1.35 × 102 Ω/ with an increasing fluence. The prepared carbon films showed a good electrical conductivity of ∼2.34 × 102 S/cm.

Electric Heating Performance of Pyrolyzed Photoresist Films Prepared by Proton Irradiation and Pyrolysis.

In this study, pyrolyzed photoresist films (PPFs) were prepared using commercial SU8 photoresist by proton irradiation and pyrolysis. SU8 thin films were irradiated with high-energy proton ions and then pyrolyzed in a tube furnace at 1000 °C under inert atmosphere. The carbonization yield of the PPFs increased with an increasing fluence due to the formation of more crosslinked network structures at a higher fluence. The electrical resistance decreased with an increasing fluence due to the higher remaining thickness and carbonization yield at a higher fluence. Therefore, the PPFs prepared at 1 × 1016 ions/cm2 showed the maximum temperature of 150 °C at 20 V and a high electric power efficiency of 1.57 mW/°C.

Effects of Silicone Oil on Electrowetting to Actuate a Digital Microfluidic Drop on Paper.

The effects of an immiscible, lubricating polydimethylsiloxane fluid, referred to as silicone oil, on the static deformation and on the dynamic motion of a water drop on paper induced by electrowetting were investigated. The deformation of a drop on a hydrophobic film of amorphous fluoropolymers top-coated with less hydrophobic silicone oil was much more predictable, reversible and reproducible than on the uncoated surface. In the dynamic tribological experiment for a sliding drop along an inclined surface, a significant decrease in the friction coefficient, with an unexpected dependency of the contact area, was observed. Based on the curve fitting analysis, the shear stress and the net friction force were estimated quantitatively. Because of the tribological effect and the reduced shear friction force of the oil film, the static and the dynamic electrowetting states of the water drop were enhanced.

Perpendicular Orientation of Diblock Copolymers Induced by Confinement between Graphene Oxide Sheets.

We have studied an orientation structure of self-assembled block copolymers (dPS-b-PMMA) of deuterated polystyrene (dPS) and poly(methyl methacrylate) (PMMA) confined between graphene oxide (GO) surfaces. The results of combination techniques, such as neutron reflectivity, time-of-flight secondary-ion mass spectrometry, grazing-incidence small-angle X-ray scattering, and scanning electron microscopy, show that self-assembled domains of the block copolymers in thin films near the GO sheets are oriented perpendicular to the surface of the GO monolayers, in contrast to the horizontal lamellar structure of the copolymer thin film in the absence of the GO monolayers. This is due to the amphiphilic nature of the GO, which leads to a nonpreferential interaction of both dPS and PMMA blocks. Double-sided confinement with the GO monolayers further extends the ordering behavior of the dPS-b-PMMA thin films. Continuous vertical orientation of the block copolymer thin films is also obtained in the presence of alternating GO layers within thick copolymer films.

Synthesis of a Graphene-Like Nanofilm from Polyacrylonitrile.

There are various different approaches in synthesizing graphene including chemical vapor deposition (CVD) and solid-phase method, where gas or solid type carbon source, to be converted into graphene, interacts with transition metals such as nickel and copper. When any thin nickel layer coated atop the polyacrylonitrile (PAN) film is pyrolyzed at a sufficiently high temperature, it is impossible to grow a continuous graphene film with a large area owing to dewetting, which has restricted the subsequent utilization in practical applications. Herein, we suggest a method to synthesize a continuous graphene-like nanofilm with a nickel coated thin PAN film through pyrolysis at 750 to 800 °C in a high-vacuum furnace without a reductive gas flow. The graphene-like nanofilm obtained was characterized using Raman spectroscopy, Raman mapping, field-emission scanning electron microscopy, X-ray photoelectron spectroscopy, and field-emission transmission electron microscopy.

Simple and Biocompatible Ion Beam Micropatterning of a Cell-Repellent Polymer on Cell-Adhesive Surfaces to Manipulate Cell Adhesion.

In this paper, the simple and biocompatible micropatterning of cell-repellent poly(N-isopropylacrylamide) (PNIPAAm) on a cell-adhesive substrate by ion beam micropatterning to control cell adhesion is described. Cell-repellent PNIPAAm films spin-coated on cell-adhesive tissue culture polystyrene (TCPS) substrates were selectively irradiated by energetic proton ions at various fluences through a pattern mask, and subsequently developed to create the micropatterns of PNIPAAm. Well-defined negative-type PNIPAAm micropatterns were successfully created on the TCPS substrates at fluences higher than 5 x 10¹4 ions/cm², and their chemical properties were dependent on the fluence. Moreover, based on the results of the protein adsorption and in-vitro cell culture tests, 200 µm well-defined micropatterns of mammalian cells were clearly formed on the PNIPAAm-micropatterned TCPS substrates though the preferential adsorption and growth of cells on the TCPS regions due to the strong cell-repellency of PNIPAAm.

Data from crosslinked PS honeycomb thin film by deep UV irradiation.

Thin polystyrene (PS) films with highly ordered honeycomb pattern were successfully fabricated by an improved phase separation method. The PS film was successfully crosslinked after applying a deep UV irradiation. This work presents a proof of crosslinking PS by characterizing ATR-FTIR, TGA and the wetting property of the honeycomb films, which were prepared using a solvent/non-solvent ratio of 90/10, before and after 6 h of UV irradiation.

Direct patterning of poly(acrylic acid) on polymer surfaces by ion beam lithography for the controlled adhesion of mammalian cells.

Poly(acrylic acid) (PAA)-patterned polystyrene (PS) substrates were prepared by ion beam lithography to control cell behaviors of mouse fibroblasts and human embryonic kidney cells. Thin PAA films spin-coated on non-biological PS substrates were selectively irradiated with energetic proton ions through a pattern mask. The irradiated substrates were developed with deionized water to generate negative-type PAA patterns. The surface characteristics of the resulting PAA-patterned PS surface, such as surface morphology, chemical structure and composition and wettability, were investigated. Well-defined 100 µm PAA patterns were effectively formed on relatively hydrophobic PS substrates by ion beam lithography at higher fluences than 5 × 10(14) ions/cm(2). Moreover, based on the in vitro cell culture test, cells were adhered and proliferated favorably onto hydrophilic PAA regions separated by hydrophobic PS regions on the PAA-patterned PS substrates, and thereby leading to the formation of well-defined cell patterns.

Active digital microfluidic paper chips with inkjet-printed patterned electrodes.

Active, paper-based, microfluidic chips driven by electrowetting are fabricated and demonstrated for reagent transport and mixing. Instead of using the passive capillary force on the pulp to actuate a flow of a liquid, a group of digital drops are transported along programmed trajectories above the electrodes printed on low-cost paper, which should allow point-of-care production and diagnostic activities in the future.

Actuation of digital micro drops by electrowetting on open microfluidic chips fabricated in photolithography.

Basic manipulations of discrete liquid drops on opened microfluidic chips based on electrowetting on dielectrics were described. While most developed microfluidic chips are closed systems equipped with a top plate to cover mechanically and to contact electrically to drop samples, our chips are opened systems with a single plate without any electric contact to drops directly. The chips consist of a linear array of patterned electrodes at 1.8 mm pitch was fabricated on a glass plate coated with thin hydrophobic and dielectric layers by using various methods including photolithography, spin coating and ion sputtering. Several actuations such as lateral oscillation, colliding mergence and translational motion for 3-10 µL water drops have been demonstrated satisfactory. All these kinetic performances of opened chips were similar to those of closed chip systems, indicating superiority of a none-contact method for the transport of drops on opened microfluidic chips actuated by using electrowetting technique.

The fabrication of patterned gold nanoparticle arrays via selective ion irradiation and plasma treatment.

A simple and facile method for the patterning of gold nanoparticles (GNPs) was described via selective ion irradiation and oxygen plasma etching. Thin Pluronic films containing HAuCI4 as the precursor of GNPs were selectively irradiated through a pattern mask with 200 keV proton ions to generate GNP-embedded Pluronic patterns. The Pluronic was then removed by an oxygen plasma etching process for the pattern formation of GNPs. Based on the results of the UV-Vis, FE-SEM, and EDX analyses, 50 µm negative-tone line patterns of the GNP-embedded Pluronic were successfully generated at a fluence of less than 1 x 10(16) ions/cm2. The changes in the morphology and elemental composition of the formed GNP-embedded Pluronic patterns with different time periods of oxygen plasma etching were investigated using an FE-SEM with an EDX. The experimental results demonstrated that the patterns of GNPs were effectively generated by the oxygen plasma etching of the formed GNP-embedded Pluronic patterns for 15 min. Furthermore, the XRD results revealed that GNPs in the patterns formed by ion irradiation were further grown during the subsequent oxygen plasma etching.