Low-Profile, Large-Range Compressive Strain Sensing Using Micromanufactured CNT Micropillar Arrays.

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 (∼300 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.

Differences in water and vapor transport through angstrom-scale pores in atomically thin membranes.

The transport of water through nanoscale capillaries/pores plays a prominent role in biology, ionic/molecular separations, water treatment and protective applications. However, the mechanisms of water and vapor transport through nanoscale confinements remain to be fully understood. Angstrom-scale pores (~2.8-6.6 Å) introduced into the atomically thin graphene lattice represent ideal model systems to probe water transport at the molecular-length scale with short pores (aspect ratio ~1-1.9) i.e., pore diameters approach the pore length (~3.4 Å) at the theoretical limit of material thickness. Here, we report on orders of magnitude differences (~80×) between transport of water vapor (~44.2-52.4 g m-2 day-1 Pa-1) and liquid water (0.6-2 g m-2 day-1 Pa-1) through nanopores (~2.8-6.6 Å in diameter) in monolayer graphene and rationalize this difference via a flow resistance model in which liquid water permeation occurs near the continuum regime whereas water vapor transport occurs in the free molecular flow regime. We demonstrate centimeter-scale atomically thin graphene membranes with up to an order of magnitude higher water vapor transport rate (~5.4-6.1 × 104 g m-2 day-1) than most commercially available ultra-breathable protective materials while effectively blocking even sub-nanometer (>0.66 nm) model ions/molecules.

Kinetic Control of Angstrom-Scale Porosity in 2D Lattices for Direct Scalable Synthesis of Atomically Thin Proton Exchange Membranes.

Angstrom-scale pores introduced into atomically thin 2D materials offer transformative advances for proton exchange membranes in several energy applications. Here, we show that facile kinetic control of scalable chemical vapor deposition (CVD) can allow for direct formation of angstrom-scale proton-selective pores in monolayer graphene with significant hindrance to even small, hydrated ions (K+ diameter ∼6.6 Å) and gas molecules (H2 kinetic diameter ∼2.9 Å). We demonstrate centimeter-scale Nafion|Graphene|Nafion membranes with proton conductance ∼3.3-3.8 S cm-2 (graphene ∼12.7-24.6 S cm-2) and H+/K+ selectivity ∼6.2-44.2 with liquid electrolytes. The same membranes show proton conductance ∼4.6-4.8 S cm-2 (graphene ∼39.9-57.5 S cm-2) and extremely low H2 crossover ∼1.7 × 10-1 - 2.2 × 10-1 mA cm-2 (∼0.4 V, ∼25 °C) with H2 gas feed. We rationalize our findings via a resistance-based transport model and introduce a stacking approach that leverages combinatorial effects of interdefect distance and interlayer transport to allow for Nafion|Graphene|Graphene|Nafion membranes with H+/K+ selectivity ∼86.1 (at 1 M) and record low H2 crossover current density ∼2.5 × 10-2 mA cm-2, up to ∼90% lower than state-of-the-art ionomer Nafion membranes ∼2.7 × 10-1 mA cm-2 under identical conditions, while still maintaining proton conductance ∼4.2 S cm-2 (graphene stack ∼20.8 S cm-2) comparable to that for Nafion of ∼5.2 S cm-2. Our experimental insights enable functional atomically thin high flux proton exchange membranes with minimal crossover.

Limiting Mechanisms and Scaling of Electrostatically Controlled Adhesion of Soft Nanocomposite Surfaces for Robotic Gripping.

Surfaces with switchable adhesive properties are employed by robots to quickly grip and release objects and thereby to perform dexterous manipulation and locomotion tasks. Robotic grippers with switchable adhesion have been developed using structured polymers and electrostatic mechanisms. However, manipulating delicate items can be challenging as this requires strong, switchable gripping forces that do not damage the target object. Soft nanocomposite electroadhesives (SNEs) were recently introduced as an option for handling such objects. The technology integrates an electrostatic adhesion mechanism into a mechanically compliant surface formed from dielectric-coated carbon nanotubes (CNTs) to ensure soft contact with target objects. In this study we explore the scaling of the electrostatic adhesion of SNEs, toward their potential application in macroscale grasping and manipulation. We measure electroadhesive pressures on millimeter-scale areas of up to ∼20 kPa with an on/off adhesion ratio of ∼700. Based on the measured forces and simple modeling, we conclude that the maximum achievable SNE adhesion forces are determined by dielectric breakdown in the insulating coating and surrounding air. Consequently, the SNE surface behaves as a parallel capacitor plate placed at an effective distance of 2.9 µm from the target object, despite being in contact with the target and therefore having the contacting CNTs separated from the surface by ∼2 nm dielectric coating. This mechanistic understanding of soft nanocomposite electroadhesives outlines the capabilities of the technology and informs their design for advanced manufacturing applications.

Facile Size-Selective Defect Sealing in Large-Area Atomically Thin Graphene Membranes for Sub-Nanometer Scale Separations.

Atomically thin graphene with a high-density of precise subnanometer pores represents the ideal membrane for ionic and molecular separations. However, a single large-nanopore can severely compromise membrane performance and differential etching between pre-existing defects/grain boundaries in graphene and pristine regions presents fundamental limitations. Here, we show for the first time that size-selective interfacial polymerization after high-density nanopore formation in graphene not only seals larger defects (>0.5 nm) and macroscopic tears but also successfully preserves the smaller subnanometer pores. Low-temperature growth followed by mild UV/ozone oxidation allows for facile and scalable formation of high-density (4-5.5 × 1012 cm-2) useful subnanometer pores in the graphene lattice. We demonstrate scalable synthesis of fully functional centimeter-scale nanoporous atomically thin membranes (NATMs) with water (∼0.28 nm) permeance ∼23× higher than commercially available membranes and excellent rejection to salt ions (∼0.66 nm, >97% rejection) as well as small organic molecules (∼0.7-1.5 nm, ∼100% rejection) under forward osmosis.

Soft nanocomposite electroadhesives for digital micro- and nanotransfer printing.

Automated handling of microscale objects is essential for manufacturing of next-generation electronic systems. Yet, mechanical pick-and-place technologies cannot manipulate smaller objects whose surface forces dominate over gravity, and emerging microtransfer printing methods require multidirectional motion, heating, and/or chemical bonding to switch adhesion. We introduce soft nanocomposite electroadhesives (SNEs), comprising sparse forests of dielectric-coated carbon nanotubes (CNTs), which have electrostatically switchable dry adhesion. SNEs exhibit 40-fold lower nominal dry adhesion than typical solids, yet their adhesion is increased >100-fold by applying 30 V to the CNTs. We characterize the scaling of adhesion with surface morphology, dielectric thickness, and applied voltage and demonstrate digital transfer printing of films of Ag nanowires, polymer and metal microparticles, and unpackaged light-emitting diodes.

Dynamics of Liquid Transfer from Nanoporous Stamps in High-Resolution Flexographic Printing.

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.

Assessment and control of the impermeability of graphene for atomically thin membranes and barriers.

Two-dimensional materials such as graphene offer fundamentally transformative opportunities in membrane separations and as impermeable barriers, but the lack of facile methods to assess and control its 'impermeability' critically limits progress. Here we show that a simple etch of the growth catalyst (Cu) through defects in monolayer graphene synthesized by chemical vapor deposition (CVD) can be used to effectively assess graphene quality for membrane/barrier applications. Using feedback from the method to tune synthesis, we realize graphene with nearly no nanometer-scale defects as assessed by diffusion measurements, in contrast to commercially available graphene that is largely optimized for electronic applications. Interestingly, we observe clear evidence of leakage through larger defects associated with wrinkles in graphene, which are selectively sealed to realize centimeter-scale atomically thin barriers exhibiting <2% mass transport compared to the graphene support. Our work provides a facile method to assess and control the 'impermeability' of graphene and shows that future work should be directed towards the control of leakage associated with wrinkles.

Molecular Sieving Across Centimeter-Scale Single-Layer Nanoporous Graphene Membranes.

Molecular sieving across atomically thin nanoporous graphene is predicted to enable superior gas separation performance compared to conventional membranes. Although molecular sieving has been demonstrated across a few pores in microscale graphene membranes, leakage through nonselective defects presents a major challenge toward realizing selective membranes with high densities of pores over macroscopic areas. Guided by multiscale gas transport modeling of nanoporous graphene membranes, we designed the porous support beneath the graphene to isolate small defects and minimize leakage through larger defects. Ion bombardment followed by oxygen plasma etching was used to produce subnanometer pores in graphene at a density of ∼1011 cm-2. Gas permeance measurements demonstrate selectivity that exceeds the Knudsen effusion ratio and scales with the kinetic diameter of the gas molecules, providing evidence of molecular sieving across centimeter-scale nanoporous graphene. The extracted nanoporous graphene performance is comparable to or exceeds the Robeson limit for polymeric gas separation membranes, confirming the potential of nanoporous graphene membranes for gas separations.

Fundamental transport mechanisms, fabrication and potential applications of nanoporous atomically thin membranes.

Graphene and other two-dimensional materials offer a new approach to controlling mass transport at the nanoscale. These materials can sustain nanoscale pores in their rigid lattices and due to their minimum possible material thickness, high mechanical strength and chemical robustness, they could be used to address persistent challenges in membrane separations. Here we discuss theoretical and experimental developments in the emerging field of nanoporous atomically thin membranes, focusing on the fundamental mechanisms of gas- and liquid-phase transport, membrane fabrication techniques and advances towards practical application. We highlight potential functional characteristics of the membranes and discuss applications where they are expected to offer advantages. Finally, we outline the major scientific questions and technological challenges that need to be addressed to bridge the gap from theoretical simulations and proof-of-concept experiments to real-world applications.

Nanoporous Atomically Thin Graphene Membranes for Desalting and Dialysis Applications.

Dialysis is a ubiquitous separation process in biochemical processing and biological research. State-of-the-art dialysis membranes comprise a relatively thick polymer layer with tortuous pores, and suffer from low rates of diffusion leading to extremely long process times (often several days) and poor selectivity, especially in the 0-1000 Da molecular weight cut-off range. Here, the fabrication of large-area (cm2 ) nanoporous atomically thin membranes (NATMs) is reported, by transferring graphene synthesized using scalable chemical vapor deposition (CVD) to polycarbonate track-etched supports. After sealing defects introduced during transfer/handling by interfacial polymerization, a facile oxygen-plasma etch is used to create size-selective pores (≤1 nm) in the CVD graphene. Size-selective separation and desalting of small model molecules (≈200-1355 Da) and proteins (≈14 000 Da) are demonstrated, with ≈1-2 orders of magnitude increase in permeance compared to state-of-the-art commercial membranes. Rapid diffusion and size-selectivity in NATMs offers transformative opportunities in purification of drugs, removal of residual reactants, biochemical analytics, medical diagnostics, therapeutics, and nano-bio separations.

Single-Layer Graphene Membranes Withstand Ultrahigh Applied Pressure.

High mechanical strength is essential for pressure-driven membrane separations with nanoporous single-layer graphene, but its ability to withstand high pressures remains to be demonstrated. We monitored failure of centimeter-scale single-layer graphene membranes on porous supports subjected to high pressures. Consistent with theory, the membranes were found to withstand higher pressures when placed on porous supports with smaller pore diameters, but failure occurred over a surprisingly broad range of pressures, attributed to heterogeneous susceptibility to failure at wrinkles, defects, and slack in the suspended graphene. Remarkably, nonwrinkled areas withstood pressure exceeding 100 bar at which many kinds of membrane suffer from compaction. Our study shows that single-layer graphene membranes can sustain ultrahigh pressure especially if the effect of wrinkles is isolated using supports with small pores and suggests the potential for the use of single-layer graphene in high-pressure membrane separations.

Knudsen effusion through polymer-coated three-layer porous graphene membranes.

Graphene membranes have the potential to exceed the permeance and selectivity limits of conventional gas separation membranes. Realizing this potential in practical systems relies on overcoming numerous scalability challenges, such as isolating or sealing permeable defects in macroscopic areas of graphene that can compromise performance and developing methods to create high densities of selective pores over large areas. This study focuses on a centimeter-scale membrane design, where leakage is reduced by substrate selection, permeable polymer film coating, and stacking of three independent layers of graphene, while (selective) pores are created by high density ion bombardment. The three-layer graphene provides high resistance to gas flow, which decreases with ion bombardment and results in selectivity consistent with Knudsen effusion. The results suggest that the permeable pores created in three layer graphene were larger than those required for molecular sieving and that designs based on single layer graphene may lend themselves more easily to molecular sieving of gases.

Selective Nanoscale Mass Transport across Atomically Thin Single Crystalline Graphene Membranes.

Atomically thin single crystals, without grain boundaries and associated defect clusters, represent ideal systems to study and understand intrinsic defects in materials, but probing them collectively over large area remains nontrivial. In this study, the authors probe nanoscale mass transport across large-area (≈0.2 cm2 ) single-crystalline graphene membranes. A novel, polymer-free picture frame assisted technique, coupled with a stress-inducing nickel layer is used to transfer single crystalline graphene grown on silicon carbide substrates to flexible polycarbonate track etched supports with well-defined cylindrical ≈200 nm pores. Diffusion-driven flow shows selective transport of ≈0.66 nm hydrated K+ and Cl- ions over ≈1 nm sized small molecules, indicating the presence of selective sub-nanometer to nanometer sized defects. This work presents a framework to test the barrier properties and intrinsic quality of atomically thin materials at the sub-nanometer to nanometer scale over technologically relevant large areas, and suggests the potential use of intrinsic defects in atomically thin materials for molecular separations or desalting.

Heterogeneous sub-continuum ionic transport in statistically isolated graphene nanopores.

Graphene and other two-dimensional materials offer a new class of ultrathin membranes that can have atomically defined nanopores with diameters approaching those of hydrated ions. These nanopores have the smallest possible pore volumes of any ion channel, which, due to ionic dehydration and electrokinetic effects, places them in a novel transport regime and allows membranes to be created that combine selective ionic transport with ultimate permeance and could lead to separations and sensing applications. However, experimental characterization and understanding of sub-continuum ionic transport in nanopores below 2 nm is limited. Here we show that isolated sub-2 nm pores in graphene exhibit, in contrast to larger pores, diverse transport behaviours consistent with ion transport over a free-energy barrier arising from ion dehydration and electrostatic interactions. Current-voltage measurements reveal that the conductance of graphene nanopores spans three orders of magnitude and that they display distinct linear, voltage-activated or rectified current-voltage characteristics and different cation-selectivity profiles. In rare cases, rapid, voltage-dependent stochastic switching is observed, consistent with the presence of a dissociable group in the pore vicinity. A modified Nernst-Planck model incorporating ion hydration and electrostatic effects quantitatively matches the observed behaviours.

Water filtration using plant xylem.

Effective point-of-use devices for providing safe drinking water are urgently needed to reduce the global burden of waterborne disease. Here we show that plant xylem from the sapwood of coniferous trees--a readily available, inexpensive, biodegradable, and disposable material--can remove bacteria from water by simple pressure-driven filtration. Approximately 3 cm(3) of sapwood can filter water at the rate of several liters per day, sufficient to meet the clean drinking water needs of one person. The results demonstrate the potential of plant xylem to address the need for pathogen-free drinking water in developing countries and resource-limited settings.

Selective ionic transport through tunable subnanometer pores in single-layer graphene membranes.

We report selective ionic transport through controlled, high-density, subnanometer diameter pores in macroscopic single-layer graphene membranes. Isolated, reactive defects were first introduced into the graphene lattice through ion bombardment and subsequently enlarged by oxidative etching into permeable pores with diameters of 0.40 ± 0.24 nm and densities exceeding 10(12) cm(-2), while retaining structural integrity of the graphene. Transport measurements across ion-irradiated graphene membranes subjected to in situ etching revealed that the created pores were cation-selective at short oxidation times, consistent with electrostatic repulsion from negatively charged functional groups terminating the pore edges. At longer oxidation times, the pores allowed transport of salt but prevented the transport of a larger organic molecule, indicative of steric size exclusion. The ability to tune the selectivity of graphene through controlled generation of subnanometer pores addresses a significant challenge in the development of advanced nanoporous graphene membranes for nanofiltration, desalination, gas separation, and other applications.

Implications of permeation through intrinsic defects in graphene on the design of defect-tolerant membranes for gas separation.

Gas transport through intrinsic defects and tears is a critical yet poorly understood phenomenon in graphene membranes for gas separation. We report that independent stacking of graphene layers on a porous support exponentially decreases flow through defects. On the basis of experimental results, we develop a gas transport model that elucidates the separate contributions of tears and intrinsic defects on gas leakage through these membranes. The model shows that the pore size of the porous support and its permeance critically affect the separation behavior, and reveals the parameter space where gas separation can be achieved regardless of the presence of nonselective defects, even for single-layer membranes. The results provide a framework for understanding gas transport in graphene membranes and guide the design of practical, selectively permeable graphene membranes for gas separation.

Mechanisms of molecular permeation through nanoporous graphene membranes.

We present an investigation of molecular permeation of gases through nanoporous graphene membranes via molecular dynamics simulations; four different gases are investigated, namely helium, hydrogen, nitrogen, and methane. We show that in addition to the direct (gas-kinetic) flux of molecules crossing from the bulk phase on one side of the graphene to the bulk phase on the other side, for gases that adsorb onto the graphene, significant contribution to the flux across the membrane comes from a surface mechanism by which molecules cross after being adsorbed onto the graphene surface. Our results quantify the relative contribution of the bulk and surface mechanisms and show that the direct flux can be described reasonably accurately using kinetic theory, provided the latter is appropriately modified assuming steric molecule-pore interactions, with gas molecules behaving as hard spheres of known kinetic diameters. The surface flux is negligible for gases that do not adsorb onto graphene (e.g., He and H2), while for gases that adsorb (e.g., CH4 and N2) it can be on the order of the direct flux or larger. Our results identify a nanopore geometry that is permeable to hydrogen and helium, is significantly less permeable to nitrogen, and is essentially impermeable to methane, thus validating previous suggestions that nanoporous graphene membranes can be used for gas separation. We also show that molecular permeation is strongly affected by pore functionalization; this observation may be sufficient to explain the large discrepancy between simulated and experimentally measured transport rates through nanoporous graphene membranes.

Selective molecular transport through intrinsic defects in a single layer of CVD graphene.

We report graphene composite membranes with nominal areas more than 25 mm(2) fabricated by transfer of a single layer of CVD graphene onto a porous polycarbonate substrate. A combination of pressure-driven and diffusive transport measurements provides evidence of size-selective transport of molecules through the membrane, which is attributed to the low-frequency occurrence of intrinsic 1-15 nm diameter pores in the CVD graphene. Our results present the first step toward the realization of practical membranes that use graphene as the selective material.