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γ-Graphyne is the most symmetric sp2/sp1 allotrope of carbon, which can be viewed as graphene uniformly expanded through the insertion of two-carbon acetylenic units between all the aromatic rings. To date, synthesis of bulk γ-graphyne has remained a challenge. We here report the synthesis of multilayer γ-graphyne through crystallization-assisted irreversible cross-coupling polymerization. A comprehensive characterization of this new carbon phase is described, including synchrotron powder X-ray diffraction, electron diffraction, lateral force microscopy, Raman spectroscopy, infrared spectroscopy, and cyclic voltammetry. Experiments indicate that γ-graphyne is a 0.48 eV band gap semiconductor, with a hexagonal a-axis spacing of 6.88 Å and an interlayer spacing of 3.48 Å, which is consistent with theoretical predictions. The observed crystal structure has an aperiodic sheet stacking. The material is thermally stable up to 240 °C but undergoes transformation at higher temperatures. While conventional 2D polymerization and reticular chemistry rely on error correction through reversibility, we demonstrate that a periodic covalent lattice can be synthesized under purely kinetic control. The reported methodology is scalable and inspires extension to other allotropes of the graphyne family.
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We here show that infiltrated bridging agents can convert inexpensively fabricated graphene platelet sheets into high-performance materials, thereby avoiding the need for a polymer matrix. Two types of bridging agents were investigated for interconnecting graphene sheets, which attach to sheets by either π-π bonding or covalent bonding. When applied alone, the π-π bonding agent is most effective. However, successive application of the optimized ratio of π-π bonding and covalent bonding agents provides graphene sheets with the highest strength, toughness, fatigue resistance, electrical conductivity, electromagnetic interference shielding efficiency, and resistance to ultrasonic dissolution. Raman spectroscopy measurements of stress transfer to graphene platelets allow us to decipher the mechanisms of property improvement. In addition, the degree of orientation of graphene platelets increases with increasing effectiveness of the bonding agents, and the interlayer spacing increases. Compared with other materials that are strong in all directions within a sheet, the realized tensile strength (945 MPa) of the resin-free graphene platelet sheets was higher than for carbon nanotube or graphene platelet composites, and comparable to that of commercially available carbon fiber composites. The toughness of these composites, containing the combination of π-π bonding and covalent bonding, was much higher than for these other materials having high strengths for all in-plane directions, thereby opening the path to materials design of layered nanocomposites using multiple types of quantitatively engineered chemical bonds between nanoscale building blocks.
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We report a new dry-state technique for non-contact patterning of nanostructured conducting materials, and demonstrate its use for carbon nanotube forests and freestanding sheets of carbon nanotubes, graphene, graphene sponge, and MXene. This method uses self-generated electron-emission pulses (â¼20 ns) in air. On a substrate-tip separation scale of 10 to 20 nm, the few molecules of gas at atmospheric pressure enables electron-emission-based interaction between a sharp tungsten tip and elements of nanostructured materials. Using the advantages of field enhancement at sharp ends of nanostructured materials, the discharge voltage is reduced to 25-30 V, depending upon the materials density. This method causes largely non-oxidative sequential decomposition of nanostructure elements neighboring the tungsten tip. The main decomposition mechanism is thermal dissociation facilitated by Joule heating and electrostatic removal of debris. The non-contact-based patterning of nanomaterials can be as fast as 10 cm s-1. The resulting precisely patterned structures (<200 nm) are largely free of foreign contaminants, thermal impact and sub-surface structural changes.
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Lightweight artificial muscle fibers that can match the large tensile stroke of natural muscles have been elusive. In particular, low stroke, limited cycle life, and inefficient energy conversion have combined with high cost and hysteretic performance to restrict practical use. In recent years, a new class of artificial muscles, based on highly twisted fibers, has emerged that can deliver more than 2,000 J/kg of specific work during muscle contraction, compared with just 40 J/kg for natural muscle. Thermally actuated muscles made from ordinary polymer fibers can deliver long-life, hysteresis-free tensile strokes of more than 30% and torsional actuation capable of spinning a paddle at speeds of more than 100,000 rpm. In this perspective, we explore the mechanisms and potential applications of present twisted fiber muscles and the future opportunities and challenges for developing twisted muscles having improved cycle rates, efficiencies, and functionality. We also demonstrate artificial muscle sewing threads and textiles and coiled structures that exhibit nearly unlimited actuation strokes. In addition to robotics and prosthetics, future applications include smart textiles that change breathability in response to temperature and moisture and window shutters that automatically open and close to conserve energy.
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Materiais Biomiméticos , Músculos , Materiais Biomiméticos/química , Fenômenos Mecânicos , Contração Muscular , Músculos/fisiologia , Nanotubos de Carbono/análise , Nanotubos de Carbono/química , Polímeros , Resistência à Tração , Têxteis/análiseRESUMO
The combination of smooth, continuous sound spectra produced by a sound source having no vibrating parts, a nanoscale thickness of a flexible active layer and the feasibility of creating large, conformal projectors provoke interest in thermoacoustic phenomena. However, at low frequencies, the sound pressure level (SPL) and the sound generation efficiency of an open carbon nanotube sheet (CNTS) is low. In addition, the nanoscale thickness of fragile heating elements, their high sensitivity to the environment and the high surface temperatures practical for thermoacoustic sound generation necessitate protective encapsulation of a freestanding CNTS in inert gases. Encapsulation provides the desired increase of sound pressure towards low frequencies. However, the protective enclosure restricts heat dissipation from the resistively heated CNTS and the interior of the encapsulated device. Here, the heat dissipation issue is addressed by short pulse excitations of the CNTS. An overall increase of energy conversion efficiency by more than four orders (from 10-5 to 0.1) and the SPL of 120 dB re 20 µPa @ 1 m in air and 170 dB re 1 µPa @ 1 m in water were demonstrated. The short pulse excitation provides a stable linear increase of output sound pressure with substantially increased input power density (>2.5 W cm-2). We provide an extensive experimental study of pulse excitations in different thermodynamic regimes for freestanding CNTSs with varying thermal inertias (single-walled and multiwalled with varying diameters and numbers of superimposed sheet layers) in vacuum and in air. The acoustical and geometrical parameters providing further enhancement of energy conversion efficiency are discussed.
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Carbon nanotube (CNT) aerogel sheets produce smooth-spectra sound over a wide frequency range (1-10(5) Hz) by means of thermoacoustic (TA) sound generation. Protective encapsulation of CNT sheets in inert gases between rigid vibrating plates provides resonant features for the TA sound projector and attractive performance at needed low frequencies. Energy conversion efficiencies in air of 2% and 10% underwater, which can be enhanced by further increasing the modulation temperature. Using a developed method for accurate temperature measurements for the thin aerogel CNT sheets, heat dissipation processes, failure mechanisms, and associated power densities are investigated for encapsulated multilayered CNT TA heaters and related to the thermal diffusivity distance when sheet layers are separated. Resulting thermal management methods for high applied power are discussed and deployed to construct efficient and tunable underwater sound projector for operation at relatively low frequencies, 10 Hz-10 kHz. The optimal design of these TA projectors for high-power SONAR arrays is discussed.
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Carbon nanotubes (CNTs) can generate smooth-spectra sound emission over a wide frequency range (1-10(5) Hz) by means of thermoacoustics (TA). However, in the low frequencies f, where the need for large area sound projectors is high, the sound generation efficiency η of open CNT sheets is low, since η [proportionality] f(2). Together with this problem, the nanoscale thickness of CNT sheets, their high sensitivity to the environment and the high surface temperatures useful for TA sound generation are other drawbacks, which we address here by protective encapsulation of free-standing CNT sheets in inert gases. We provide an extensive experimental study of such closed systems for different thermodynamic regimes and rationalize our observations within a basic theoretical framework. The observed sound pressure levels for encapsulated argon filled TA transducers (130 dB in air and 200 dB underwater in the near field at 5 cm distance, and 100 and 170 dB in the far field at 1 m distance) are Q times higher than those for open systems, where Q is the resonant quality factor of the thin enclosure plates. Moreover, the sound generation efficiency of the encapsulated system increases toward low frequencies (η [proportionality] 1/f(2)). Another method to increase η in the low frequency region is by modulation of the applied high frequency carrier current with a low frequency resonant envelope. This approach enables sound generation at the frequency of the applied current without the need for additional energy-consuming biasing. The acoustical and geometrical parameters providing further increases in efficiency and transduction performance for resonant systems are discussed.
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The prospect of electronic circuits that are stretchable and bendable promises tantalizing applications such as skin-like electronics, roll-up displays, conformable sensors and actuators, and lightweight solar cells. The preparation of highly conductive and highly extensible materials remains a challenge for mass production applications, such as free-standing films or printable composite inks. Here we present a nanocomposite material consisting of carbon nanotubes, ionic liquid, silver nanoparticles, and polystyrene-polyisoprene-polystyrene having a high electrical conductivity of 3700 S cm(-1) that can be stretched to 288% without permanent damage. The material is prepared as a concentrated dispersion suitable for simple processing into free-standing films. For the unstrained state, the measured thermal conductivity for the electronically conducting elastomeric nanoparticle film is relatively high and shows a non-metallic temperature dependence consistent with phonon transport, while the temperature dependence of electrical resistivity is metallic. We connect an electric fan to a DC power supply using the films to demonstrate their utility as an elastomeric electronic interconnect. The huge strain sensitivity and the very low temperature coefficient of resistivity suggest their applicability as strain sensors, including those that operate directly to control motors and other devices.
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Hemiterpenos/química , Líquidos Iônicos/química , Látex/química , Nanocompostos/química , Nanotubos de Carbono/química , Poliestirenos/química , Prata/química , Elasticidade , Condutividade Elétrica , Modelos Moleculares , Nanocompostos/ultraestrutura , Nanopartículas/química , Nanopartículas/ultraestrutura , Condutividade TérmicaRESUMO
Polycrystalline graphene grown by chemical vapor deposition (CVD) on metals and transferred onto arbitrary substrates has line defects and disruptions such as wrinkles, ripples, and folding that adversely affect graphene transport properties through the scattering of the charge carriers. It is found that graphene assembled with metal nanowires (NWs) dramatically decreases the resistance of graphene films. Graphene/NW films with a sheet resistance comparable to that of the intrinsic resistance of graphene have been obtained and tested as a transparent electrode replacing indium tin oxide films in electrochromic (EC) devices. The successful integration of such graphene/NW films into EC devices demonstrates their potential for a wide range of optoelectronic device applications.
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Stretching a coiled carbon nanotube (CNT) yarn can provide large, reversible electrochemical capacitance changes, which convert mechanical energy to electricity. Here, it is shown that the performance of these "twistron" harvesters can be increased by optimizing the alignment of precursor CNT forests, plastically stretching the precursor twisted yarn, applying much higher tensile loads during precoiling twist than for coiling, using electrothermal pulse annealing under tension, and incorporating reduced graphene oxide nanoplates. The peak output power for a 1 and a 30 Hz sinusoidal deformation are 0.73 and 3.19 kW kg-1 , respectively, which are 24- and 13-fold that of previous twistron harvesters at these respective frequencies. This performance at 30 Hz is over 12-fold that of other prior-art mechanical energy harvesters for frequencies between 0.1 and 600 Hz. The maximum energy conversion efficiency is 7.2-fold that for previous twistrons. Twistron anode and cathode yarn arrays are stretched 180° out-of-phase by locating them in the negative and positive compressibility directions of hinged wine-rack frames, thereby doubling the output voltage and reducing the input mechanical energy.
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The single-beam mirage effect, also known as photothermal deflection, is studied using a free-standing, highly aligned carbon nanotube aerogel sheet as the heat source. The extremely low thermal capacitance and high heat transfer ability of these transparent forest-drawn carbon nanotube sheets enables high frequency modulation of sheet temperature over an enormous temperature range, thereby providing a sharp, rapidly changing gradient of refractive index in the surrounding liquid or gas. The advantages of temperature modulation using carbon nanotube sheets are multiple: in inert gases the temperature can reach > 2500 K; the obtained frequency range for photothermal modulation is ~100 kHz in gases and over 100 Hz in high refractive index liquids; and the heat source is transparent for optical and acoustical waves. Unlike for conventional heat sources for photothermal deflection, the intensity and phase of the thermally modulated beam component linearly depends upon the beam-to-sheet separation over a wide range of distances. This aspect enables convenient measurements of accurate values for thermal diffusivity and the temperature dependence of refractive index for both liquids and gases. The remarkable performance of nanotube sheets suggests possible applications as photo-deflectors and for switchable invisibility cloaks, and provides useful insights into their use as thermoacoustic projectors and sonar. Visibility cloaking is demonstrated in a liquid.
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The application of solid-state fabricated carbon nanotube sheets as thermoacoustic projectors is extended from air to underwater applications, thereby providing surprising results. While the acoustic generation efficiency of a liquid immersed nanotube sheet is profoundly degraded by nanotube wetting, the hydrophobicity of the nanotube sheets in water results in an air envelope about the nanotubes that increases pressure generation efficiency a hundred-fold over that obtained by immersion in wetting alcohols. Due to nonresonant sound generation, the emission spectrum of a liquid-immersed nanotube sheet varies smoothly over a wide frequency range, 1-10(5) Hz. The sound projection efficiency of nanotube sheets substantially exceeds that of much heavier and thicker ferroelectric acoustic projectors in the important region below about 4 kHz, and this performance advantage increases with decreasing frequency. While increasing thickness by stacking sheets eventually degrades performance due to decreased ability to rapidly transform thermal energy to acoustic pulses, use of tandem stacking of separated nanotube sheets (that are addressed with phase delay) eliminates this problem. Encapsulating the nanotube sheet projectors in argon provided attractive performance at needed low frequencies, as well as a realized energy conversion efficiency in air of 0.2%, which can be enhanced by increasing the modulation of temperature.
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The extremely high thermal conductivity of individual carbon nanotubes, predicted theoretically and observed experimentally, has not yet been achieved for large nanotube assemblies. Resistances at tube-tube interconnections and tube-electrode interfaces have been considered the main obstacles for effective electronic and heat transport. Here we show that, even for infinitely long and perfect nanotubes with well-designed tube-electrode interfaces, excessive radial heat radiation from nanotube surfaces and quenching of phonon modes in large bundles are additional processes that substantially reduce thermal transport along nanotubes. Equivalent circuit simulations and an experimental self-heating 3omega technique were used to determine the peculiarities of anisotropic heat flow and thermal conductivity of single MWNTs, bundled MWNTs and aligned, free-standing MWNT sheets. The thermal conductivity of individual MWNTs grown by chemical vapor deposition and normalized to the density of graphite is much lower (kappa(MWNT) = 600 +/- 100 W m(-1) K(-1)) than theoretically predicted. Coupling within MWNT bundles decreases this thermal conductivity to 150 W m(-1) K(-1). Further decrease of the effective thermal conductivity in MWNT sheets to 50 W m(-1) K(-1) comes from tube-tube interconnections and sheet imperfections like dangling fiber ends, loops and misalignment of nanotubes. Optimal structures for enhancing thermal conductivity are discussed.
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Here it is experimentally shown that Co nanoparticles with a single-domain crystal structure support a plasmon resonance at approximately 280 nm with better quality than gold nanoparticle resonance in the visible. Magnetic nature of the nanoparticles suggests a new type of these plasmons. The exchange interaction of electrons splits the energy bands between spin-up electrons and spin-down electrons. It makes it possible for coexistence of two independent channels of conductivity as well as two independent plasmons in the same nanoparticle with very different electron relaxation. Indeed, the density of empty states in a partially populated d-band is high, resulting in a large relaxation rate of the spin-down conduction electrons and consequently in low quality of the plasmon resonance. In contrast, the majority electrons with a completely filled d-band do not provide final states for the scattering processes of the conduction spin-up electrons, therefore supporting a high quality plasmon resonance. The scattering without spin flip is required to keep these two plasmons independent.
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Higher-efficiency, lower-cost refrigeration is needed for both large- and small-scale cooling. Refrigerators using entropy changes during cycles of stretching or hydrostatic compression of a solid are possible alternatives to the vapor-compression fridges found in homes. We show that high cooling results from twist changes for twisted, coiled, or supercoiled fibers, including those of natural rubber, nickel titanium, and polyethylene fishing line. Using opposite chiralities of twist and coiling produces supercoiled natural rubber fibers and coiled fishing line fibers that cool when stretched. A demonstrated twist-based device for cooling flowing water provides high cooling energy and device efficiency. Mechanical calculations describe the axial and spring-index dependencies of twist-enhanced cooling and its origin in a phase transformation for polyethylene fibers.
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Thermoacoustic performance of thin freestanding sheets of carbonized poly(acrylonitrile) and polybenzimidazole nanofibers are studied as promising candidates for thermophones. We analyze thermodynamic properties of sheets using transport parameters of single nanofibers and their aligned and randomly electrospun thin film assemblies. The electrical and thermal conductivities, thermal diffusivity, heat capacity, and infrared blackbody radiation are investigated to extract the heat exchange coefficient and enhance the energy conversion efficiency. Spectral and power dependencies of sound pressure in air are compared with carbon nanotube sheets and theoretical prediction. Despite lower thermoacoustic performance compared to that of CNT sheets, the mechanical strength and cost-effective production technology of thermophones make them very attractive for large-size sound projectors. The advantages of carbonized electrospun polymer nanofiber sheets are in the low frequency domain (<1000 Hz), where the large thermal diffusion length diminishes the thermal inertia of thick (â¼200 nm) nonbundled fibers and the high intrinsic thermal conductivity of fibers enhances the heat exchange coefficient. Applications of thermoacoustic projectors for loudspeakers, high power SONAR arrays, and sound cancellation are discussed.
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The fabrication and characterization of highly flexible textiles are reported. These textiles can harvest thermal energy from temperature gradients in the desirable through-thickness direction. The tiger yarns containing n- and p-type segments are woven to provide textiles containing n-p junctions. A high power output of up to 8.6 W m(-2) is obtained for a temperature difference of 200 °C.
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Thermophones are highly promising for applications such as high-power SONAR arrays, flexible loudspeakers, and noise cancellation devices. So far, freestanding carbon nanotube aerogel sheets provide the most attractive performance as a thermoacoustic heat source. However, the limited accessibility of large-size freestanding carbon nanotube aerogel sheets and other even more exotic materials recently investigated hampers the field. We describe alternative materials for a thermoacoustic heat source with high-energy conversion efficiency, additional functionalities, environmentally friendly, and cost-effective production technologies. We discuss the thermoacoustic performance of alternative nanostructured materials and compare their spectral and power dependencies of sound pressure in air. We demonstrate that the heat capacity of aerogel-like nanostructures can be extracted by a thorough analysis of the sound pressure spectra. The study presented here focuses on engineering thermal gradients in the vicinity of nanostructures and subsequent heat dissipation processes from the interior of encapsulated thermoacoustic projectors. Applications of thermoacoustic projectors for high-power SONAR arrays, sound cancellation, and optimal thermal design, regarding enhanced energy conversion efficiency, are discussed.
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By combining a graphene layer and aligned multiwalled carbon nanotube (MWNT) sheets in two different configurations, i) graphene on the top of MWNTs and ii) MWNTs on the top of the graphene, it is demonstrated that optical, electrical, and electromechanical properties of the resulting hybrid films depend on configurations.