High‐Nanofiller‐Content Graphene Oxide–Polymer Nanocomposites via Vacuum‐Assisted Self‐Assembly

Highly ordered, homogeneous polymer nanocomposites of layered graphene oxide are prepared using a vacuum‐assisted self‐assembly (VASA) technique. In VASA, all components (nanofiller and polymer) are pre‐mixed prior to assembly under a flow, making it compatible with either hydrophilic poly(vinyl alcohol) (PVA) or hydrophobic poly(methyl methacrylate) (PMMA) for the preparation of composites with over 50 wt% filler. This process is complimentary to layer‐by‐layer assembly, where the assembling components are required to interact strongly (e.g., via Coulombic attraction). The nanosheets within the VASA‐assembled composites exhibit a high degree of order with tunable intersheet spacing, depending on the polymer content. Graphene oxide–PVA nanocomposites, prepared from water, exhibit greatly improved modulus values in comparison to films of either pure PVA or pure graphene oxide. Modulus values for graphene oxide–PMMA nanocomposites, prepared from dimethylformamide, are intermediate to those of the pure components. The differences in structure, modulus, and strength can be attributed to the gallery composition, specifically the hydrogen bonding ability of the intercalating species     

Bioinspired Fabrication of Superhydrophobic Graphene Films by Two‐Beam Laser Interference

Reported here is a bioinspired fabrication of superhydrophobic graphene surfaces by means of two‐beam laser interference (TBLI) treatment of graphene oxide (GO) films. Microscale grating‐like structures with tunable periods and additional nanoscale roughness are readily created on graphene films due to laser induced ablation effect. Synchronously, abundant hydrophilic oxygen‐containing groups (OCGs) on GO sheets can be drastically removed after TBLI treatment, which lower its surface energy significantly. The synergistic effect of micro‐nanostructuring and the OCGs removal endows the resultant graphene films with unique superhydrophobicity. Additionally, dual TBLI treatment with 90° rotation is implemented to fabricate superhydrophobic graphene films with two‐dimensional grating‐like structures that can effectively avoid the anisotropic hydrophobicity originated from the grooved structures. Moreover, the superhydrophobic graphene films become conductive due to the laser reduction effect. Unique optical characteristics including transmission diffraction and brilliant structural color are also observed due to the presence of periodic microstructures. As a mask‐free, chemical‐free, and cost‐effective method, the TBLI processing of GO may open up a new way to biomimetic graphene surfaces, and thus hold great promise for the development of novel graphene‐based microdevices.     

Thickness Dependence of the Mechanical Properties of Free‐Standing Graphene Oxide Papers

Graphene oxide (GO) papers are candidates for structural materials in modern technology due to their high specific strength and stiffness. The relationship between their mechanical properties and structure needs to be systematically investigated before they can be applied to the broad range fields where they have potential. Herein, the mechanical properties of GO papers with various thicknesses (0.5–100 μm) are investigated using bulge and tensile test methods; this includes the Young's modulus, fracture strength, fracture strain, and toughness. The Young's modulus, fracture strength, and toughness are found to decrease with increasing thickness, with the first two exhibiting differences by a factor of four. In contrast, the fracture strain slightly increases with thickness. Transmission electron, scanning electron, and atomic force microscopy indicate that the mechanical properties vary with thickness due to variations in the inner structure and surface morphology, such as crack formation and surface roughness. Thicker GO papers are weaker because they contain more voids that are produced during the fabrication process. Surface wrinkles and residual stress are found to result in increased fracture strain. Determination of this structure–property relationship provide improved guidelines for the use of GO‐based thin‐film materials in mechanical structures.     

A Controllable Self‐Assembly Method for Large‐Scale Synthesis of Graphene Sponges and Free‐Standing Graphene Films

A simple method to prepare large‐scale graphene sponges and free‐standing graphene films using a speed vacuum concentrator is presented. During the centrifugal evaporation process, the graphene oxide (GO) sheets in the aqueous suspension are assembled to generate network‐linked GO sponges or a series of multilayer GO films, depending on the temperature of a centrifugal vacuum chamber. While sponge‐like bulk GO materials (GO sponges) are produced at 40 °C, uniform free‐standing GO films of size up to 9 cm² are generated at 80 °C. The thickness of GO films can be controlled from 200 nm to 1 µm based on the concentration of the GO colloidal suspension and evaporation temperature. The synthesized GO films exhibit excellent transparency, typical fluorescent emission signal, and high flexibility with a smooth surface and condensed density. Reduced GO sponges and films with less than 5 wt% oxygen are produced through a thermal annealing process at 800 °C with H₂/Ar flow. The structural flexibility of the reduced GO sponges, which have a highly porous, interconnected, 3D network, as well as excellent electrochemical properties of the reduced GO film with respect to electrode kinetics for the [Fe(CN)₆]^3?/4? redox system, are demonstrated.     

Layer‐by‐Layer Assembly of 3D Tissue Constructs with Functionalized Graphene

Carbon‐based nanomaterials have been considered promising candidates to mimic certain structure and function of native extracellular matrix materials for tissue engineering. Significant progress has been made in fabricating carbon nanoparticle‐incorporated cell culture substrates, but only a limited number of studies have been reported on the development of 3D tissue constructs using these nanomaterials. Here, a novel approach to engineer 3D multilayer constructs using layer‐by‐layer (LbL) assembly of cells separated with self‐assembled graphene oxide (GO)‐based thin films is presented. The GO‐based structures are shown to serve as cell adhesive sheets that effectively facilitate the formation of multilayer cell constructs with interlayer connectivity. By controlling the amount of GO deposited in forming the thin films, the thickness of the multilayer tissue constructs could be tuned with high cell viability. Specifically, this approach could be useful for creating dense and tightly connected cardiac tissues through the co‐culture of cardiomyocytes and other cell types. In this work, the fabrication of stand‐alone multilayer cardiac tissues with strong spontaneous beating behavior and programmable pumping properties is demonstrated. Therefore, this LbL‐based cell construct fabrication approach, utilizing GO thin films formed directly on cell surfaces, has great potential in engineering 3D tissue structures with improved organization, electrophysiological function, and mechanical integrity.     

Highly Stable Graphene‐Based Multilayer Films Immobilized via Covalent Bonds and Their Applications in Organic Field‐Effect Transistors

Highly stable graphene oxide (GO)‐based multilayered ultrathin films can be covalently immobilized on solid supports through a covalent‐based method. It is demonstrated that when (3‐aminopropyl) trimethoxysilane (APTMS), which works as a covalent cross‐linking agent, and GO nanosheets are assembled in an layer‐by‐layer (LBL) manner, GO nanosheets can be covalently grafted on the solid substrate successfully to produce uniform multilayered (APTMS/GO)N films over large‐area surfaces. Compared with conventional noncovalent LBL films constructed by electrostatic interactions, those assembled using this covalent‐based method display much higher stability and reproducibility. Upon thermal annealing‐induced reduction of the covalent (APTMS/GO)N films, the obtained reduced GO (RGO) films, (APTMS/RGO)N, preserve their basic structural characteristics. It is also shown that the as‐prepared covalent (APTMS/RGO)N multilayer films can be used as highly stable source/drain electrodes in organic field‐effect transistors (OFETs). When the number of bilayers of the (APTMS/RGO)N film exceeds 2 (ca. 2.7 nm), the OFETs based on (APTMS/RGO)N electrodes display much better electrical performance than devices based on 40 nm Au electrodes. The covalent protocol proposed may open up new opportunities for the construction of graphene‐based ultrathin films with excellent stability and reproducibility, which are desired for practical applications that require withstanding of multistep post‐production processes.     

Toughness and Fracture Properties in Nacre‐Mimetic Clay/Polymer Nanocomposites

Nacre inspires researchers by combining stiffness with toughness by its unique microstructure of aligned aragonite platelets. This brick‐and‐mortar structure of reinforcing platelets separated with thin organic matrix has been replicated in numerous mimics that can be divided into two categories: microcomposites with aligned metal oxide microplatelets in polymer matrix, and nanocomposites with self‐assembled nanoplatelets—usually clay or graphene oxide—and polymer. While microcomposites have shown exceptional fracture toughness, current fabrication methods have limited nacre‐mimetic nanocomposites to thin films where fracture properties remained unexplored. Yet, fracture resistance is the defining property of nacre, therefore centrally important in any mimic. Furthermore, to make use of these properties in applications, bulk materials are required. Here, up to centimeter‐thick nacre‐mimetic clay/polymer nanocomposites are produced by the lamination of self‐assembled films. The aligned clay nanoplatelets are separated by poly(vinyl alcohol) matrix, with 10⁶–10⁷ nanoplatelets on top of each other in the bulk plates. Fracture testing shows crack deflection and a fracture toughness of 3.4 MPa m^1/2, not far from nacre. Flexural tests show high stiffness (25 GPa) and strength (220 MPa) that, despite the hydrophilic constituents, are not substantially affected by exposure to humidity.     

A Large‐Area,Flexible, and Flame‐Retardant Graphene Paper

Similar to the paper‐making process, the efficient flame retardant graphene paper is conveniently obtained by using graphene oxide (GO) and hexachlorocyclotriphosphazene (HCCP) aqueous pulp. The “paper pulp” can also conceivably be used as ink to make other hydrophilic films become flame retardant paper. Further, the as‐prepared reduced GO‐HCCP paper (RGO‐HCCP paper), compared with GO‐HCCP paper, can maintain its intact structure for a longer time in an ethanol flame. As a consequence of these preparation methods, the bearing temperature of the as‐prepared graphene papers shows a significant increase.     

Enhancement of Modulus,Strength, and Toughness in Poly(methyl methacrylate)‐Based Composites by the Incorporation of Poly(methyl methacrylate)‐Functionalized Nanotubes

Poly(methyl methacrylate) (PMMA)‐functionalized multiwalled carbon nanotubes are prepared by in situ polymerization. Infrared absorbance studies reveal covalent bonding between polymer strands and the nanotubes. These treated nanotubes are blended with pure PMMA in solution before drop‐casting to form composite films. Increases in Young's modulus, breaking strength, ultimate tensile strength, and toughness of ×1.9, ×4.7, ×4.6, and ×13.7, respectively, are observed on the addition of less than 0.5 wt % of nanotubes. Effective reinforcement is only observed up to a nanotube content of approximately 0.1 vol %. Above this volume fraction, all mechanical parameters tend to fall off, probably due to nanotube aggregation. In addition, scanning electron microscopy (SEM) studies of composite fracture surfaces show a polymer layer coating the nanotubes after film breakage. The fact that the polymer and not the interface fails suggests that functionalization results in an extremely high polymer/nanotube interfacial shear strength.     

Dry‐Type Artificial Muscles Based on Pendent Sulfonated Chitosan and Functionalized Graphene Oxide for Greatly Enhanced Ionic Interactions and Mechanical Stiffness

Biopolymer‐based artificial muscles are promising candidates for biomedical applications and smart electronic textiles due to their multifaceted advantages like natural abundance, eco‐friendliness, cost‐effectiveness, easy chemical modification and high electical reactivity. However, the biopolymer‐based actuators are showing relatively low actuation performance compared with synthetic electroactive polymers because of inadequate mechanical stiffness, low ionic conductivity and ionic exchange capacity (IEC), and poor durability over long‐term activation. This paper reports a high‐performance electro‐active nano‐biopolymer based on pendent sulfonated chitosan (PSC) and functionalized graphene oxide (GO), exhibiting strong electro‐chemo‐mechanical interations with ionic liquid (IL) in open air environment. The proposed GO‐PSC‐IL nano‐biopolymer membrane shows an icnreased tensile strength and ionic exchange capacity of up to 44.8% and 83.1%, respectively, and increased ionic conductivity of over 18 times, resulting in two times larger bending actuation than the pure chitosan actuator under electrical input signals. Eventually, the GO‐PSC‐IL actuators could show robust and high‐performance actuation even at the very low applied voltages that are required in realistic applications.     

Bioinspired Design Criteria for Damage‐Resistant Materials with Periodically Varying Microstructure

Many biological materials, such as bone, nacre, or certain deep‐sea glass sponges, have a hierarchical structure that makes them stiff, tough, and damage tolerant. Different structural features contributing to these exceptional properties have been identified, but a common motif of these materials, the periodic arrangement of structural components with strongly varying stiffness, has not gained sufficient attention. Here we show that the periodicity of the material properties is one of the dominant reasons for the high fracture resistance of these structures and their tolerance to short cracks. If the composite architecture fulfills certain design rules, which are derived in this paper, the stiff structure becomes fracture resistant and, most of all, flaw tolerant. This architectural criterion inspired from nature provides useful guidelines for the design of defect‐tolerant resistant man‐made materials.     

Self‐Propagating Domino‐like Reactions in Oxidized Graphite

Graphite oxide (GO) has received extensive interest as a precursor for the bulk production of graphene‐based materials. Here, the highly energetic nature of GO, noted from the self‐propagating thermal deoxygenating reaction observed in solid state, is explored. Although the resulting graphene product is quite stable against combustion even in a natural gas flame, its thermal stability is significantly reduced when contaminated with potassium salt by‐products left from GO synthesis. In particular, the contaminated GO becomes highly flammable. A gentle touch with a hot soldering iron can trigger violent, catastrophic, total combustion of such GO films, which poses a serious fire hazard. This highlights the need for efficient sample purification methods. Typically, purification of GO is hindered by its tendency to gelate as the pH value increases during rinsing. A two‐step, acid–acetone washing procedure is found to be effective for suppressing gelation and thus facilitating purification. Salt‐induced flammability is alarming for the fire safety of large‐scale manufacturing, processing, and storage of GO materials. However, the energy released from the deoxygenation of GO can also be harnessed to drive new reactions for creating graphene‐based hybrid materials. Through such domino‐like reactions, graphene sheets decorated with metal and metal oxide particles are synthesized using GO as the in situ power source. Enhanced electrochemical capacitance is observed for graphene sheets loaded with RuO₂ nanoparticles.     

Stiff and Transparent Multilayer Thin Films Prepared Through Hydrogen‐Bonding Layer‐by‐Layer Assembly of Graphene and Polymer

Due to their exceptional orientation of 2D nanofillers, layer‐by‐layer (LbL) assembled polymer/graphene oxide thin films exhibit unmatched mechanical performance relative to any conventionally produced counterparts with similar composition. Unprecedented mechanical property improvement, by replacing graphene oxide with pristine graphene, is demonstrated in this work. Polyvinylpyrrolidone‐stabilized graphene platelets are alternately deposited with poly(acrylic acid) using hydrogen bonding assisted LbL assembly. Transmission electron microscopy imaging and the Halpin‐Tsai model are used to demonstrate, for the first time, that intact graphene can be processed from water to generate polymer nanocomposite thin films with simultaneous parallel‐alignment, high packing density, and exfoliation. A multilayer thin film with only 3.9 vol% of highly exfoliated, and structurally intact graphene, increases the elastic modulus (E) of a polymer multilayer thin film by 322% (from 1.41 to 4.81 GPa), while maintaining visible light transmittance of ≈90%. This is one of the greatest improvements in elastic modulus ever reported for a graphene‐filled polymer nanocomposite with a glassy (E > 1 GPa) matrix. The technique described here provides a powerful new tool to improve nanocomposite properties (mechanical, gas transport, etc.) that can be universally applied to a variety of polymer matrices and 2D nanoplatelets.     

π‐Conjugated Molecules Crosslinked Graphene‐Based Ultrathin Films and Their Tunable Performances in Organic Nanoelectronics

Graphene‐based ultrathin films with tunable performances, controlled thickness, and high stability are crucial for their uses. The currently existing protocols, however, could hardly simultaneously meet these requirements. Using amino‐substituted π‐conjugated compounds, including 1,4‐diaminobenzene (DABNH2), benzidine (BZDNH2), and 5,10,15,20‐tetrakis (4‐aminophenyl)‐21H,23H‐porphine (TPPNH2), as cross‐linkages, a new protocol through which graphene oxide (GO) nanosheets can be anchored on solid supports with a high stability and controlled thickness via a layer‐by‐layer method is presented. A thermal annealing leads to the reduction of the films, and the qualities of the samples can be inherited by the as‐produced reduced GO films (RGO). When RGO films are integrated as source/drain electrodes in OFETs, tunable performances can be realized. The devices based on the BZDNH2‐crosslinked RGO electrodes exhibit similar electrical behaviors as those based on the non‐π‐conjugated compound crosslinked electrodes, while improved performances can be gained when those crosslinked by DABNH2 are used. The performances can be further improved when RGO films crosslinked by TPPNH2 are employed. This work likely paves a new avenue for graphene‐based films of tunable performances, controlled thickness, and high stability.     

Strongly‐Coupled Freestanding Hybrid Films of Graphene and Layered Titanate Nanosheets: An Effective Way to Tailor the Physicochemical and Antibacterial Properties of Graphene Film

An effective way to tailor the physicochemical properties of graphene film is developed by combining colloidal suspensions of reduced graphene oxide (rG‐O) nanosheets and exfoliated layered titanate nanosheets for the fabrication of freestanding hybrid films comprised of stacked and overlapped nanosheets. A flow‐directed filtration of such mixed colloidal suspensions yields freestanding hybrid films comprised of strongly‐coupled rG‐O and titanate nanosheets with tunable chemical composition. This is the first example of highly flexible hybrid films composed of graphene and metal oxide nanosheets. The intimate incorporation of layered titanate nanosheets into the graphene film gives rise not only to an increase of mechanical strength but also to increased surface roughness, chemical stability, and hydrophilicity; thus, the physicochemical properties of the graphene film can be tuned by hybridization with inorganic nanosheets. These freestanding hybrid films of rG‐O‐layered titanate show unprecedentedly high antibacterial property, resulting in the complete sterilization of Escherichia coli O157:H7 (≈100%) in the very short time of 15 min. The antibacterial activity of the hybrid film is far superior to that of the pure graphene film, underscoring the beneficial effect of the layered metal oxide nanosheets in improving the functionality of the graphene film.     

Epoxy Toughening with Low Graphene Loading

The toughening effects of graphene and graphene‐derived materials on thermosetting epoxies are investigated. Graphene materials with various structures and surface functional groups are incorporated into an epoxy resin by in situ polymerization. Graphene oxide (GO) and GO modified with amine‐terminated poly(butadiene‐acrylonitrile) (ATBN) are chosen to improve the dispersion of graphene nanosheets in epoxy and increase their interfacial adhesion. An impressive toughening effect is observed with less than 0.1 wt% graphene. A maximum in toughness at loadings as small as 0.02 wt% or 0.04 wt% is observed for all four types of graphene studied. An epoxy nanocomposite with ATBN‐modified GO shows a 1.5‐fold improvement in fracture toughness and a corresponding 2.4‐fold improvement in fracture energy at 0.04 wt% of graphene loading. At such low loadings, these graphene‐type materials become economically feasible components of nanocomposites. A microcrack mechanism is proposed based on microscopy of the fracture surfaces. Due to the stress concentration by graphene nanosheets, microcracks may be formed to absorb the fracture energy. However, above a certain graphene concentration, the coalescence of microcracks appears to facilitate crack propagation, lowering the fracture toughness. Crack deflection and pinning likely contribute to the slow increase in fracture toughness at higher loadings.     

Flexible Organic Photovoltaic Cells with In Situ Nonthermal Photoreduction of Spin‐Coated Graphene Oxide Electrodes

The first reduction methodology, compatible with flexible, temperature‐sensitive substrates, for the production of reduced spin‐coated graphene oxide (GO) electrodes is reported. It is based on the use of a laser beam for the in situ, non‐thermal, reduction of spin‐coated GO films on flexible substrates over a large area. The photoreduction process is one‐step, facile, and is rapidly carried out at room temperature in air without affecting the integrity of the graphene lattice or the flexibility of the underlying substrate. Conductive graphene films with a sheet resistance of as low as 700 Ω sq^?1 and transmittance of 44% can be obtained, much higher than can be achieved for flexible layers reduced by chemical means. As a proof of concept of our technique, laser‐reduced GO (LrGO) films are utilized as transparent electrodes in flexible, bulk heterojunction, organic photovoltaic (OPV) devices, replacing the traditional ITO. The devices displayed a power‐conversion efficiency of 1.1%, which is the highest reported so far for OPV device incorporating reduced GO as the transparent electrode. The in situ non‐thermal photoreduction of spin‐coated GO films creates a new way to produce flexible functional graphene electrodes for a variety of electronic applications in a process that carries substantial promise for industrial implementation.     

Molecular‐Level Dispersion of Graphene into Poly(vinyl alcohol) and Effective Reinforcement of their Nanocomposites

Despite great recent progress with carbon nanotubes and other nanoscale fillers, the development of strong, durable, and cost‐efficient multifunctional nanocomposite materials has yet to be achieved. The challenges are to achieve molecule‐level dispersion and maximum interfacial interaction between the nanofiller and the matrix at low loading. Here, the preparation of poly(vinyl alcohol) (PVA) nanocomposites with graphene oxide (GO) using a simple water solution processing method is reported. Efficient load transfer is found between the nanofiller graphene and matrix PVA and the mechanical properties of the graphene‐based nanocomposite with molecule‐level dispersion are significantly improved. A 76% increase in tensile strength and a 62% improvement of Young's modulus are achieved by addition of only 0.7 wt% of GO. The experimentally determined Young's modulus is in excellent agreement with theoretical simulation.     

Sea‐Urchin‐Inspired 3D Crumpled Graphene Balls Using Simultaneous Etching and Reduction Process for High‐Density Capacitive Energy Storage

A crumpled configuration of graphene is desirable for preventing irreversible stacking between individual nanosheets, which can be a major hurdle toward its widespread application. Herein a sea‐urchin‐shaped template approach is introduced for fabricating highly crumpled graphene balls in bulk quantities with a simple process. Simultaneous chemical etching and reduction process of graphene oxide (GO)‐encapsulated iron oxide particles results in dissolution of the core template with spiky morphology and conversion of the outer GO layers into reduced GO layers with increased hydrophobicity which remain in contact with the spiky surface of the template. After completely etching, the outer graphene layers are fully compressed into the crumpled form along with decrease in total volume by etching. The crumpled balls exhibit significantly larger surface area and good water‐dispersion stability than those of stacked reduced GO or other crumple approaches, even though they also show comparable electrical conductivity. Furthermore, they are easily assembled into 3D macroporous networks without any binders through typical processes such as solvent casting or compression molding. The graphene networks with less pore volume still have the crumpled morphology without sacrificing the properties regardless of the assembly processes, producing a promising active electrode material with high gravimetric and volumetric energy density for capacitive energy storage.     

Hierarchical Toughening of Nacre‐Like Composites

Reinforced polymer‐based composites are attractive lightweight materials for aircrafts, automobiles, and turbine blades, but still show strength and fracture toughness lower than traditional metals. An interesting approach to address this issue is to fabricate composites with structural features that absorb part of the elastic energy stored in the material during fracture through extrinsic and intrinsic toughening mechanisms behind and ahead of the crack tip, respectively. Inspired by the nacreous layer of mollusk shells, the fracture behavior of multiscale composites that combine intrinsic toughness from a brick‐and‐mortar structure connected through nanoscale mineral bridges and extrinsic toughness arising from a brittle–ductile laminate architecture at the millimeter scale are fabricated and investigated. Such a hierarchical toughening approach increases the dissipated energy by more than 30‐fold during fracture with minimal loss in stiffness and strength. Using simple energy balance arguments and fracture mechanics concepts, guidelines are established for the design of nacre‐like composites with a remarkable combination of stiffness, strength, and toughness. This demonstrates the possibility to controllably introduce toughening mechanisms at different length scales and to thus fabricate hierarchical composites with high fracture resistance in spite of the brittle nature of their main inorganic constituents.