Min Kyoon Shin

Torsional Carbon Nanotube Artificial Muscles

Carbon nanotube yarns are used to make fast, multirotational torsional actuators. Rotary motors of conventional design can be rather complex and are therefore difficult to miniaturize; previous carbon nanotube artificial muscles provide contraction and bending, but not rotation. We show that an electrolyte-filled twist-spun carbon nanotube yarn, much thinner than a human hair, functions as a torsional artificial muscle in a simple three-electrode electrochemical system, providing a reversible 15,000° rotation and 590 revolutions per minute. A hydrostatic actuation mechanism, as seen in muscular hydrostats in nature, explains the simultaneous occurrence of lengthwise contraction and torsional rotation during the yarn volume increase caused by electrochemical double-layer charge injection. The use of a torsional yarn muscle as a mixer for a fluidic chip is demonstrated.

Electrically, Chemically, and Photonically Powered Torsional and Tensile Actuation of Hybrid Carbon Nanotube Yarn Muscles

Nanotube Yarn Actuators Actuators are used to convert heat, light, or electricity into a twisting or tensile motion, and are often described as artificial muscles. Most materials that show actuation either provide larger forces with small-amplitude motions, such as the alloy NiTi, or provide larger motions with much less force, such as polymeric materials. Other problems with such actuators can include slow response times and short lifetimes. Lima et al. (p. 928, see the Perspective by Schulz) show that a range of guest-filled, twist-spun carbon nanotube yarns can be used for linear or torsional actuation, can solve the problems of speed and lifetime, and do not require electrolytes for operation. Thermally driven actuators use a guest material within carbon nanotube yarns to generate fast torsional and tensile motions. Artificial muscles are of practical interest, but few types have been commercially exploited. Typical problems include slow response, low strain and force generation, short cycle life, use of electrolytes, and low energy efficiency. We have designed guest-filled, twist-spun carbon nanotube yarns as electrolyte-free muscles that provide fast, high-force, large-stroke torsional and tensile actuation. More than a million torsional and tensile actuation cycles are demonstrated, wherein a muscle spins a rotor at an average 11,500 revolutions/minute or delivers 3% tensile contraction at 1200 cycles/minute. Electrical, chemical, or photonic excitation of hybrid yarns changes guest dimensions and generates torsional rotation and contraction of the yarn host. Demonstrations include torsional motors, contractile muscles, and sensors that capture the energy of the sensing process to mechanically actuate.

Synergistic toughening of composite fibres by self-alignment of reduced graphene oxide and carbon nanotubes

The extraordinary properties of graphene and carbon nanotubes motivate the development of methods for their use in producing continuous, strong, tough fibres. Previous work has shown that the toughness of the carbon nanotube-reinforced polymer fibres exceeds that of previously known materials. Here we show that further increased toughness results from combining carbon nanotubes and reduced graphene oxide flakes in solution-spun polymer fibres. The gravimetric toughness approaches 1,000 J g−1, far exceeding spider dragline silk (165 J g−1) and Kevlar (78 J g−1). This toughness enhancement is consistent with the observed formation of an interconnected network of partially aligned reduced graphene oxide flakes and carbon nanotubes during solution spinning, which act to deflect cracks and allow energy-consuming polymer deformation. Toughness is sensitive to the volume ratio of the reduced graphene oxide flakes to the carbon nanotubes in the spinning solution and the degree of graphene oxidation. The hybrid fibres were sewable and weavable, and could be shaped into high-modulus helical springs.

Elastomeric Conductive Composites Based on Carbon Nanotube Forests

Electrically conductive materials capable of substantial elastic stretch and bending are needed for such applications as smart clothing, flexible displays, stretchable circuits, strain gauges, implantable devices, high-stroke microelectromechanical systems, and dielectric elastomer actuators. A variety of approaches involving carbon nanotubes (CNTs) and elastic polymers have been suggested for the fabrication of conductive elastic composites. In particular, diverse active and passive electronic components have been embedded in rubber sheet by several research groups to obtain stretchable electronic devices. Sekitani et al. developed rubber-like conductive composites by mixing millimeter-long single-walled carbon nanotubes (SWNTs), an ionic liquid, and a fluorinated copolymer. The stretchability of the resulting composite was enhanced by creating perforated films with a net-shaped structure using a mechanical punching system. Cao et al. fabricated flexible electrodes by incorporating SWNTnetworks in plastics consisting of polyimide, polyurethane, and polyamic acid films. Although quite successful, these studies indicated that high loading of CNTs (or other conductive additive) was necessary to obtain a highly conducting composite. On the other hand, incorporation of high concentrations of CNTs into an elastic polymer increases the stiffness of the resulting composite and decreases its stretchability. In other words, the significant difference in the Young’s modulus of extremely rigid CNTs and the elastic polymer filler makes the creation of a highly stretchable conductive composites a challenging task. It is known that CNTs can be fabricated into macroscopic assemblies, such as mats (bucky paper), yarns, and fibers that possess useful electrical properties, and that these assemblies can be used for the fabrication of conductive polymer composites. While these assemblies are often more elastic than the individual CNTs, the achievable elastic strain range is still quite limited, normally less than 10%. We found that a combination of high stretchability and high electrical conductivity can be obtained for composites prepared from three-dimensional CNT structures, such as CNT forests (vertically aligned arrays of CNTs). Unlike previous methods involving casting CNT/ polymer dispersions as a film, our composites were prepared by the direct infiltration of multiwalled carbon nanotube (MWNT) forests with a polyurethane (PU) solution. Using this procedure, we obtained rubber-like forest/PU composites that combined high stretchability with high electrical conductivity. These composites provide highly reversible stress–strain behavior and little degradation of mechanical and electrical properties even when stretched over a wide strain range. The developed preparation procedure appears scalable for material fabrication on an industrial scale, though transition from present batchbased forest growth processes to continuous forest growth processes would be needed for applications that are price sensitive and depend on sheet weight, rather than the area of elastomeric sheet. The aligned arrays of MWNTs (MWNT forests) used in this study were grown on iron-catalyst-coated silicon wafers using a conventional chemical vapor deposition (CVD) method. Nanotubes in the forests typically had a diameter of about 10 nm; their length could be controlled across a wide range by changing the growth time and other fabrication conditions. The forest-covered area on the substrate used for the preparation of the composites typically had dimensions of about 50 100mm; the height of nanotubes in the forest was about 50mm as determined by the conventional optical microscopy. Since the nanotubes in the forests formed a three-dimensionally interconnected network, the forests were electrically conductive in all directions. The MWNT forests were infiltrated with a PU solution in N,N-dimethylformamide (DMF) using a simple drop-casting procedure, as shown in Figure 1a. The PU used was poly[4,40methylene-bis(phenyl isocyanate)-alt-1,4-butanediol/poly(butylene adipate)]. After evaporation of the solvent, we obtained about 250mm thick forest/PU composite sheets that could be peeled off the underlying Si wafer. Figure 1b shows a photograph of the MWNT/PU composite sheet taken at low magnification. One side of the prepared film facing the substrate (forest side) was black and conductive, and the other side (PU side) was white and insulating. The material was soft, flexible, and highly stretchable in the sheet plane. Figure 1c shows a SEM image of a cross-section of the composite sheet with the top ( 50mm in thickness) being the forest side and the bottom ( 200mm in thickness) being the PU side. A highmagnification image of the forest side is shown in the

Size-dependent elastic modulus of single electroactive polymer nanofibers

The authors report for the first time the size dependency of the elastic modulus of well-aligned single polymeric nanofibers. The nanofibers were fabricated from electroactive polymers (EAPs) and had an ellipsoidal cross section because of impingement between a solid surface and a polymer jet during electrospinning. Although the EAPs had very weak mechanical properties in the bulk, the elastic modulus of single EAP nanofibers increased exponentially as the diameter of the EAP nanofibers decreased to diameters of a few tens of nanometers. The elastic modulus of single nanofibers was measured using three-point bending tests employing an atomic force microscope.

Hybrid Nanomembranes for High Power and High Energy Density Supercapacitors and Their Yarn Application

We report mechanically robust, electrically conductive, free-standing, and transparent hybrid nanomembranes made of densified carbon nanotube sheets that were coated with poly(3,4-ethylenedioxythiophene) using vapor phase polymerization and their performance as supercapacitors. The hybrid nanomembranes with thickness of ~66 nm and low areal density of ~15 μg/cm(2)exhibited high mechanical strength and modulus of 135 MPa and 12.6 GPa, respectively. They also had remarkable shape recovery ability in liquid and at the liquid/air interface unlike previous carbon nanotube sheets. The hybrid nanomembrane attached on a current collector had volumetric capacitance of ~40 F/cm(3) at 100 V s(-1) (~40 and ~80 times larger than that of onion-like carbon measured at 100 V s(-1) and activated carbon measured at 20 V s(-1), respectively), and it showed rectangular shapes of cyclic voltammograms up to ~5 V s(-1). High mechanical strength and flexibility of the hybrid nanomembrane enabled twisting it into microsupercapacitor yarns with diameters of ~30 μm. The yarn supercapacitor showed stable cycling performance without a metal current collector, and its capacitance decrease was only ~6% after 5000 cycles. Volumetric energy and power density of the hybrid nanomembrane was ~70 mWh cm(-3) and ~7910 W cm(-3), and the yarn possessed the energy and power density of ~47 mWh cm(-3) and ~538 W cm(-3).

Hybrid carbon nanotube yarn artificial muscle inspired by spider dragline silk

Torsional artificial muscles generating fast, large-angle rotation have been recently demonstrated, which exploit the helical configuration of twist-spun carbon nanotube yarns. These wax-infiltrated, electrothermally powered artificial muscles are torsionally underdamped, thereby experiencing dynamic oscillations that complicate positional control. Here, using the strategy spiders deploy to eliminate uncontrolled spinning at the end of dragline silk, we have developed ultrafast hybrid carbon nanotube yarn muscles that generated a 9,800 r.p.m. rotation without noticeable oscillation. A high-loss viscoelastic material, comprising paraffin wax and polystyrene-poly(ethylene-butylene)-polystyrene copolymer, was used as yarn guest to give an overdamped dynamic response. Using more than 10-fold decrease in mechanical stabilization time, compared with previous nanotube yarn torsional muscles, dynamic mirror positioning that is both fast and accurate is demonstrated. Scalability to provide constant volumetric torsional work capacity is demonstrated over a 10-fold change in yarn cross-sectional area, which is important for upscaled applications.

Controlled magnetic nanofiber hydrogels by clustering ferritin.

We have fabricated biocompatible nanofiber hydrogels with diverse sizes of ferritin clusters according to the mixing temperature of solutions employing electrospinning. Poly(vinyl alcohol) (PVA) was used as a polymeric matrix for fabricating nanocomposites. By thermal means we controlled the interaction between the host PVA hydrogel and the protein shell on ferritin bionanoparticles to vary the size and concentration of ferritin clusters. The clustering of ferritin was based on the partial unfolding of a protein shell of ferritin. By studying the magnetic properties of the PVA/ferritin nanofibers according to the mixing temperature of the PVA/ferritin solutions, we confirmed that the clustering process of the ferritin was related to changes in the superparamagnetic properties and magnetic resonance imaging (MRI) contrast of the PVA/ferritin nanofibers. PVA/ferritin nanofiber hydrogels with diverse spatial distributions of ferritin nanoparticles are applicable as MRI-based noninvasive detectable cell culture scaffolds and as artificial muscles because of their improved superparamagnetic properties.

Reinforcement of polymeric nanofibers by ferritin nanoparticles

Poly(vinyl alcohol) (PVA) nanofibers containing bimolecular ferritin nanoparticles exhibited the enhancement of elastic modulus as compared to pure PVA nanofibers due to chemical interactions between the ferritin and the PVA matrix. The elastic modulus of the nanofibers was measured using a three-point bending test employing an atomic force microscope (AFM). To improve the reliability of the AFM measurements, uniform nanofibers were oriented linearly on an AFM calibration grating by introducing parallel subelectrodes in an electrospinning system. The length to diameter ratio of the measured nanofibers was >16. The PVA nanofibers reinforced by ferritin are applicable as artificial muscles and actuators.

Controlled assembly of polymer nanofibers: From helical springs to fully extended

We describe simple procedures for fabricating single polymeric helical nanofibers and converting these helical nanofibers into linearly oriented nanofibers using a modified electric field in an electrospinning system. Helical structures were made from a solution of poly(2-acrylamido-2-methyl-1-propanesulfonic acid) in water and ethanol by bending instability of electrospinning. By newly introducing parallel subelectrodes that change an ordinary electric field into a splitting electric field, it was elucidated that the tensional electrostatic forces caused by a modified electric field have an important effect on the transformation of helical structures.