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In supramolecular materials, multiple weak binding groups can act as a single collective unit when confined to a localized volume, thereby producing strong but dynamic bonds between material building blocks. This principle of multivalency provides a versatile means of controlling material assembly, as both the number and the type of supramolecular moieties become design handles to modulate the strength of intermolecular interactions. However, in materials with building blocks significantly larger than individual supramolecular moieties (e.g., polymer or nanoparticle scaffolds), the degree of multivalency is difficult to predict or control, as sufficiently large scaffolds inherently preclude separated supramolecular moieties from interacting. Because molecular models commonly used to examine supramolecular interactions are intrinsically unable to examine any trends or emergent behaviors that arise due to nanoscale scaffold geometry, our understanding of the thermodynamics of these massively multivalent systems remains limited. Here we address this challenge via the coassembly of polymer-grafted nanoparticles and multivalent polymers, systematically examining how multivalent scaffold size, shape, and spacing affect their collective thermodynamics. Investigating the interplay of polymer structure and supramolecular group stoichiometry reveals complicated but rationally describable trends that demonstrate how the supramolecular scaffold design can modulate the strength of multivalent interactions. This approach to self-assembled supramolecular materials thus allows for the manipulation of polymer-nanoparticle composites with controlled thermal stability, nanoparticle organization, and tailored meso- to microscopic structures. The sophisticated control of multivalent thermodynamics through precise modulation of the nanoscale scaffold geometry represents a significant advance in the ability to rationally design complex hierarchically structured materials via self-assembly.
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Direct ink writing, a versatile method of 3D and 4D printing, requires the precise placement of a nozzle just above the print surface to prevent fluid instabilities that cause deviations from the prescribed print path. But what if one could harness the instability associated with the spontaneously folding or coiling of a thin stream of viscous fluid, i.e. use the "fluid rope trick" to write specified patterns on a substrate? Here we use Deep Reinforcement Learning to derive control strategies for the motion of the extruding nozzle and thus the fluid patterns that are deposited on the surface. The method proceeds by having a learner (nozzle) repeatedly interact with the environment (a viscous filament simulator), and improves its strategy using the results of this experience. We demonstrate the outcome of the learned control instructions using experiments to manipulate a falling viscous jet and create cursive writing patterns and Pollockian paintings on substrates.
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Molecularly organized nanocomposites of polymers and carbon nanotubes (CNTs) have great promise as high-performance materials; in particular, conformal deposition of polymers can control interfacial properties for mechanical load transfer, electrical or thermal transport, or electro/chemical transduction. However, controllability of polymer-CNT interaction remains a challenge with common processing methods that combine CNTs and polymers in melt or in solution, often leading to nonuniform polymer distribution and CNT aggregation. Here, we demonstrate CNTs within net-shape sheets can be controllably coated with a conformal coating of meta-aramid by simultaneous capillary infiltration and interfacial polymerization. We determine that π-interaction between the polymer and CNTs results in chain alignment parallel to the CNT outer wall. Subsequent nucleation and growth of the precipitated aramid forms a smooth continuous layered sheath around the CNTs. These findings motivate future investigation of mechanical properties of the resulting composites, and adaptation of the in situ polymerization method to other substrates.
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Nanocompostos , Nanotubos de Carbono , Nanocompostos/química , Nanotubos de Carbono/química , Polimerização , Polímeros/químicaRESUMO
Development of a refractory selective solar absorber (RSSA) is the key to unlock high-temperature solar thermal and thermochemical conversion. The fundamental challenge of RSSA is the lack of design and fabrication guidelines to simultaneously achieve omnidirectional, broadband solar absorption and sharp spectral selectivity at the desired cutoff wavelength. Here, we realize a ruthenium-carbon nanotube (Ru-CNT) nanocomposite RSSA with multiscale nanoparticle-on-nanocavity plasmonic modes. Ru conformally coated on the sidewalls of CNTs enables a spoof surface plasmon polariton mode for spectra selectivity; Ru nanoparticles formed at the tips of CNTs enable a localized surface plasmon resonance mode and plasmon hybridization for omnidirectional broadband solar absorption. The fabricated Ru-CNT RSSA has a total solar absorption (TSA) of 96.1% with sharp spectral cutoff at 2.21 µm. The TSA is maintained at over 90% for an incident angle of 56°. Our findings therefore guide full-spectrum optical and thermal control from visible to the far-infrared.
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Materials made by directed self-assembly of colloids can exhibit a rich spectrum of optical phenomena, including photonic bandgaps, coherent scattering, collective plasmonic resonance, and wave guiding. The assembly of colloidal particles with spatial selectivity is critical for studying these phenomena and for practical device fabrication. While there are well-established techniques for patterning colloidal crystals, these often require multiple steps including the fabrication of a physical template for masking, etching, stamping, or directing dewetting. Here, the direct-writing of colloidal suspensions is presented as a technique for fabrication of iridescent colloidal crystals in arbitrary 2D patterns. Leveraging the principles of convective assembly, the process can be optimized for high writing speeds (≈600 µm s-1 ) at mild process temperature (30 °C) while maintaining long-range (cm-scale) order in the colloidal crystals. The crystals exhibit structural color by grating diffraction, and analysis of diffraction allows particle size, relative grain size, and grain orientation to be deduced. The effect of write trajectory on particle ordering is discussed and insights for developing 3D printing techniques for colloidal crystals via layer-wise printing and sintering are provided.
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Accurate quantification of trace contaminants currently requires collection, preservation, and transportation of large volumes (250-1000 mL) of water to centralized laboratories, which impedes monitoring of trace-level pollutants in many resource-limited environments. To overcome this logistical challenge, we propose a new paradigm for trace contaminant monitoring based on dry preservation: solid-phase extraction, preservation, storage, transport, and analysis of trace contaminants (SEPSTAT). We show that a few grams of low-cost, commercially available cation exchange resin can be repurposed to extract heavy metal cations from water samples even in the presence of background ions, dryly preserve these cations for at least 24 months, and release them by acid elution for accurate quantification. A compact, human-powered device incorporating the sorbent removes spiked contaminants from real water samples in a few minutes. The device can be stored and transported easily and produces a sample suitable for measurement by standard methods, predicting the original sample heavy metal concentration generally within an error of 15%. These results suggest that, by facilitating the collection, storage, handling, and transportation of water samples and by enabling cost-effective use of high-throughput capital-intensive instruments, SEPSTAT has the potential to increase the ease and reach of water quality monitoring of trace contaminants.
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Metais Pesados , Poluentes Químicos da Água , Humanos , Extração em Fase Sólida , Água , Qualidade da ÁguaRESUMO
Printing of ultrathin layers of polymeric and colloidal inks is critical for the manufacturing of electronics on nonconventional substrates such as paper and polymer films. Recently, we found that nanoporous stamps overcome key limitations of traditional polymer stamps in flexographic printing, namely, enabling the printing of ultrathin nanoparticle films with micron-scale lateral precision. Here, we study the dynamics of liquid transfer between nanoporous stamps and solid substrates. The stamps comprise forests of polymer-coated carbon nanotubes, and the surface mechanics and wettability of the stamps are engineered to imbibe colloidal inks and transfer the ink upon contact with the target substrate. By high-speed imaging during printing, we observe the dynamics of liquid spreading, which is mediated by progressing contact between the nanostructured stamp surface and by the substrate and imbibition within the stamp-substrate gap. From the final contact area, the volume of ink transfer is mediated by rupture of a capillary bridge; and, after rupture, liquid spreads to fill the area defined by a precursor film matching the stamp geometry with high precision. Via modeling of the liquid dynamics, and comparison with data, we elucidate the scale- and rate-limiting aspects of the process. Specifically, we find that the printed ink volume and resulting layer thickness are independent of contact pressure; and that printed layer thickness decreases with retraction speed. Under these conditions, nanoparticle films with controlled thickness in the <100 nm regime can be printed using nanoporous stamp flexography, at speeds commensurate with industrial printing equipment.
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Cellulose nanocrystals (CNC) are naturally-derived nanostructures of growing importance for the production of composites having attractive mechanical properties, and offer improved sustainability over purely petroleum-based alternatives. Fabrication of CNC composites typically involves extrusion of CNC suspensions and gels in a variety of solvents, in the presence of additives such as polymers and curing agents. Most studies so far have focused on aqueous CNC gels, yet the behavior of CNC-polymer gels in organic solvents is important to their wider processability. Here, we study the rheological behavior of composite polymer-CNC gels in dimethylformamide, which include additives for both UV and thermal crosslinking. Using rheometry coupled with in situ infrared spectroscopy, we show that under external shear, CNC-polymer gels display progressive and irreversible failure of the hydrogen bond network that is responsible for their pronounced elastic properties. In the absence of cross-linking additives, the polymer-CNC gels show an instantaneous but partial recovery of their viscoelasticity upon cessation of flow, whereas, the presence of additives allows the gels to recover over much longer timescale via van der Waals interactions. By exploring a broad range of shear history and CNC concentrations, we construct master curves for the temporal evolution of the viscoelastic properties of the polymer-CNC gels, illustrating universality of the observed dynamics with respect to gel composition and flow conditions. We find that polymer-CNC composite gels display a number of the distinctive features of colloidal glasses and, strikingly, that their response to the flow conditions encountered during processing can be tuned by chemical additives. These findings have implications for processing of dense CNC-polymer composites in solvent casting, 3D printing, and other manufacturing techniques.
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Understanding of the liquid imbibition dynamics in nanoporous materials is important to advances in chemical separations, phase change heat transfer, electrochemical energy storage, and diagnostic assays. We study the liquid imbibition behavior in films of ceramic-coated vertically aligned carbon nanotubes (CNTs). The nanoscale porosity of the films is tuned by conformal ceramic coating via atomic layer deposition (ALD), enabling stable liquid imbibition and precise measurement of the imbibition dynamics without capillary densification of the CNTs. We show that the imbibition rate decreases as the ceramic coating thickness increases, which effectively changes the CNT-CNT spacing and therefore decreases the permeability. We derive a model, based on Darcy's law, that incorporates an expression for the permeability of nanoscale post arrays, and we show that the model fits the experimental results with high accuracy. The tailorable porosity, along with controllable surface wettability and mechanical stability of coated CNTs, suggest their suitability for application-guided engineering, and for further investigation of imbibition behavior at finer length scales.
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The widespread potential application of vertically aligned carbon nanotube (CNT) forests have stimulated recent work on large-area chemical vapor deposition growth methods, but improved control of the catalyst particles is needed to overcome limitations to the monodispersity and packing density of the CNTs. In particular, traditional thin-film deposition methods are not ideal due to their vacuum requirements, and due to limitations in particle uniformity and density imposed by the thin-film dewetting process. Here, a continuous-feed convective self-assembly process for manufacturing uniform mono- and multi-layers of catalyst particles for CNT growth is presented. Particles are deposited from a solution of commercially available iron oxide nanoparticles, by pinning the meniscus between a blade edge and the substrate. The substrate is translated at constant velocity under the blade so the meniscus and contact angle remain fixed as the particles are deposited on the substrate. Based on design of the particle solution and tuning of the assembly parameters, a priori control of CNT diameter and packing density is demonstrated. Quantitative relationships are established between the catalyst size and density, and the CNT morphology and density. The roll-to-roll compatibility of this method, along with initial results achieved on copper foils, suggest promise for scale-up of CNT forest manufacturing at commercially relevant throughput.
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Elastocapillary self-assembly is emerging as a versatile technique to manufacture three-dimensional (3D) microstructures and complex surface textures from arrangements of micro- and nanoscale filaments. Understanding the mechanics of capillary self-assembly is essential to engineering of properties such as shape-directed actuation, anisotropic wetting and adhesion, and mechanical energy transfer and dissipation. We study elastocapillary self-assembly (herein called "capillary forming") of carbon nanotube (CNT) microstructures, combining in situ optical imaging, micromechanical testing, and finite element modeling. By imaging, we identify sequential stages of liquid infiltration, evaporation, and solid shrinkage, whose kinetics relate to the size and shape of the CNT microstructure. We couple these observations with measurements of the orthotropic elastic moduli of CNT forests to understand how the dynamic of shrinkage of the vapor-liquid interface is coupled to the compression of the forest. We compare the kinetics of shrinkage to the rate of evporation from liquid droplets having the same size and geometry. Moreover, we show that the amount of shrinkage during evaporation is governed by the ability of the CNTs to slip against one another, which can be manipulated by the deposition of thin conformal coatings on the CNTs by atomic layer deposition (ALD). This insight is confirmed by finite element modeling of pairs of CNTs as corrugated beams in contact and highlights the coupled role of elasticity and friction in shrinkage and stability of nanoporous solids. Overall, this study shows that nanoscale porosity can be tailored via the filament density and adhesion at contact points, which is important to the development of lightweight multifunctional materials.
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Nanoestruturas/química , Nanotubos de Carbono/química , Elasticidade , Cinética , Tamanho da Partícula , Propriedades de SuperfícieRESUMO
Engineering the density of carbon nanotube (CNT) forest microstructures is vital to applications such as electrical interconnects, micro-contact probes, and thermal interface materials. For CNT forests on centimeter-scale substrates, weight and volume can be used to calculate density. However, this is not suitable for smaller samples, including individual microstructures, and moreover does not enable mapping of spatial density variations within the forest. We demonstrate that the relative mass density of individual CNT microstructures can be measured by optical attenuation, with spatial resolution equaling the size of the focused spot. For this, a custom optical setup was built to measure the transmission of a focused laser beam through CNT microstructures. The transmittance was correlated with the thickness of the CNT microstructures by Beer-Lambert-Bouguer law to calculate the attenuation coefficient. We reveal that the density of CNT microstructures grown by CVD can depend on their size, and that the overall density of arrays of microstructures is affected significantly by run-to-run process variations. Further, we use the technique to quantify the change in CNT microstructure density due to capillary densification. This is a useful and accessible metrology technique for CNTs in future microfabrication processes, and will enable direct correlation of density to important properties such as stiffness and electrical conductivity.
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Surfaces coated with nanoscale filaments such as silicon nanowires and carbon nanotubes are potentially compelling for high-performance battery and capacitor electrodes, photovoltaics, electrical interconnects, substrates for engineered cell growth, dry adhesives, and other smart materials. However, many of these applications require a wet environment or involve wet processing during their synthesis. The capillary forces introduced by these wet environments can lead to undesirable aggregation of nanoscale filaments, but control of capillary forces can enable manipulation of the filaments into discrete aggregates and novel hierarchical structures. Recent studies suggest that the elastocapillary self-assembly of nanofilaments can be a versatile and scalable means to build complex and robust surface architectures. To enable a wider understanding and use of elastocapillary self-assembly as a fabrication technology, we give an overview of the underlying fundamentals and classify typical implementations and surface designs for nanowires, nanotubes, and nanopillars made from a wide variety of materials. Finally, we discuss exemplary applications and future opportunities to realize new engineered surfaces by the elastocapillary self-assembly of nanofilaments.
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Nanoestruturas/química , Nanotubos de Carbono/química , Nanofios/químicaRESUMO
Ultraviolet (UV) printing of photopolymers is a widely adopted manufacturing method because of its high resolution and throughput. However, available printable photopolymers are typically thermosets, resulting in challenges in postprocessing and recycling of printed structures. Here, we present a new process called interfacial photopolymerization (IPP) which enables photopolymerization printing of linear chain polymers. In IPP, a polymer film is formed at the interface between two immiscible liquids, one containing a chain-growth monomer and the other containing a photoinitiator. We demonstrate the integration of IPP in a proof-of-concept projection system for printing of polyacrylonitrile (PAN) films and rudimentary multi-layer shapes . IPP shows in-plane and out-of-plane resolutions comparable to conventional photoprinting methods. Cohesive PAN films with number-average molecular weights greater than 15 kg mol-1 are obtained, and to our knowledge this is the first report of photopolymerization printing of PAN. A macrokinetics model of IPP is developed to elucidate the transport and reaction rates involved and evaluate how reaction parameters affect film thickness and print speed. Last, demonstration of IPP in a multilayer scheme suggests its suitabiliy for three-dimensional printing of linear-chain polymers.
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Tactile sensors, or sensors that collect measurements through touch, have versatile applications in a wide range of fields including robotic gripping, intelligent manufacturing, and biomedical technology. Hoping to match the ability of human hands to sense physical changes in objects through touch, engineers have experimented with a variety of materials from soft polymers to hard ceramics, but so far, all have fallen short. A grand challenge for developers of "human-like" bionic tactile sensors is to be able to sense a wide range of strains while maintaining the low profile necessary for compact integration. Here, we developed a low-profile tactile sensor (â¼300 µm in height) based on patterned, vertically aligned carbon nanotubes (PVACNT) that can repetitively sense compressive strains of up to 75%. Upon compression, reversible changes occur in the points of contact between CNTs, producing measurable changes in electrical admittance. By patterning VACNT pillars with different aspect ratios and pitch sizes, we engineered the range and resolution of strain sensing, suggesting that CNT-based tactile sensors can be integrated according to device specifications.
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Chlorosulfonic acid and oleum are ideal solvents for enabling the transformation of disordered carbon nanotubes (CNTs) into precise and highly functional morphologies. Currently, processing these solvents using extrusion techniques presents complications due to chemical compatibility, which constrain equipment and substrate material options. Here, we present a novel acid solvent system based on methanesulfonic or p-toluenesulfonic acids with low corrosivity, which form true solutions of CNTs at concentrations as high as 10 g/liter (≈0.7 volume %). The versatility of this solvent system is demonstrated by drop-in application to conventional manufacturing processes such as slot die coating, solution spinning continuous fibers, and 3D printing aerogels. Through continuous slot coating, we achieve state-of-the-art optoelectronic performance (83.6 %T and 14 ohm/sq) at industrially relevant production speeds. This work establishes practical and efficient means for scalable processing of CNT into advanced materials with properties suitable for a wide range of applications.
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Additive manufacturing (AM) has gained significant attention due to its ability to drive technological development as a sustainable, flexible, and customizable manufacturing scheme. Among the various AM techniques, direct ink writing (DIW) has emerged as the most versatile 3D printing technique for the broadest range of materials. DIW allows printing of practically any material, as long as the precursor ink can be engineered to demonstrate appropriate rheological behavior. This technique acts as a unique pathway to introduce design freedom, multifunctionality, and stability simultaneously into its printed structures. Here, a comprehensive review of DIW of complex 3D structures from various materials, including polymers, ceramics, glass, cement, graphene, metals, and their combinations through multimaterial printing is presented. The review begins with an overview of the fundamentals of ink rheology, followed by an in-depth discussion of the various methods to tailor the ink for DIW of different classes of materials. Then, the diverse applications of DIW ranging from electronics to food to biomedical industries are discussed. Finally, the current challenges and limitations of this technique are highlighted, followed by its prospects as a guideline toward possible futuristic innovations.
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We demonstrate the fabrication of horizontally aligned carbon nanotube (HA-CNT) networks by spatially programmable folding, which is induced by self-directed liquid infiltration of vertical CNTs. Folding is caused by a capillary buckling instability and is predicted by the elastocapillary buckling height, which scales with the wall thickness as t(3/2). The folding direction is controlled by incorporating folding initiators at the ends of the CNT walls, and the initiators cause a tilt during densification which precedes buckling. By patterning these initiators and specifying the wall geometry, we control the dimensions of HA-CNT patches over 2 orders of magnitude and realize multilayered and multidirectional assemblies. Multidirectional HA-CNT patterns are building blocks for custom design of nanotextured surfaces and flexible circuits.
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A simple, reliable and potentially cost-effective composite film casting procedure is presented using the evaporation of solvent (water) from a dilute mixture of multiwalled carbon nanotubes (MWCNTs) and polyethylene oxide (PEO) polymer. It is found that the fabrication method develops excellent dispersion of MWCNTs in PEO confirmed by morphology observations, final crystallinity of polymer (amorphous) and a lower percolation threshold (closer to theoretical value) as well as higher electrical conductivity. A film thickness prediction model is derived based upon the fact that final film thickness is mainly dependent upon the dimensions of the casting mold and the loading of the MWCNTs and polymer. This simple model provides important insight that the material loss and the actual density of the base polymer are critical factors making the current casting method truly cost effective and controlling final thickness.
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Binder jet additive manufacturing (BJAM) is capable of fabricating complex three-dimensional components from a variety of material classes. Understanding the fundamentals of BJAM, including spreading of thin layers of powder, powder-binder interactions, and post-processing is critical to develop robust process parameters for BJAM. Toward meeting these needs, this work presents the design, fabrication, and qualification of a testbed for modular, mechanized, BJAM. The testbed seeks to replicate the operating conditions of commercial AM equipment and features fully programmable motion control including powder spreading using a precision roller mechanism, powder supply via a vibrating hopper, and gantry positioning of an inkjet printhead. The inkjet deposition system allows for the use of variable nozzle diameters, the exploration of novel binder compositions, and full control of jetting parameters. Validation of the accuracy and repeatability of the machine and its subsystems, as well as the fabrication of exemplary stainless steel components, are described. The precision engineered testbed can therefore enable the study of the BJAM process, exploration of novel binder compositions, and processing of custom powders to further scientific research and industrial applicability of BJAM.