Fast and Strong Carbon Nanotube Yarn Artificial Muscles by Electro-osmotic Pump.

Previous electrochemically powered yarn muscles cannot be usefully operated between extreme negative and extreme positive potentials, since generated stresses during anion injection and cation injection partially cancel because they are in the same direction. We here report an ionomer-infiltrated hybrid carbon nanotube (CNT) yarn muscle that shows unipolar stress behavior in the sense that stress generation between extreme potentials is additive, resulting in an enhanced stress generation. Moreover, the stress generated by this muscle unexpectedly increases with the potential scan rate, which contradicts the fact that scan-rate-induced stress decreases for neat CNT muscles. It is revealed by the electro-osmotic pump effect that the effective ion size injected into the muscle increases with an increase in the scan rate. We demonstrate an electrochemically powered gel-elastomer-yarn muscle adhesive that generates and delivers muscle-contraction-mimicking stimulation to a target tissue.

Development of Carbon Nanotube Yarn Supercapacitors and Energy Storage for Integrated Structural Health Monitoring.

Developing efficient, sustainable, and high-performance energy storage systems is essential for advancing various industries, including integrated structural health monitoring. Carbon nanotube yarn (CNTY) supercapacitors have the potential to be an excellent solution for this purpose because they offer unique material properties such as high capacitance, electrical conductivity, and energy and power densities. The scope of the study included fabricating supercapacitors using various materials and characterizing them to determine the capacitive properties, energy, and power densities. Experimental studies were conducted to investigate the energy density and power density behavior of CNTYs embedded in various electrochemical-active matrices to monitor the matrices' power process and the CNTY supercapacitors' life-cyclic response. The results showed that the CNTY supercapacitors displayed excellent capacitive behavior, with nearly rectangular CV curves across a range of scan rates. The energy density and power density of the supercapacitors fluctuated between a minimum of 3.89 Wh/kg and 8 W/kg while the maximum was between 6.46 Wh/kg and 13.20 W/kg. These CNTY supercapacitors are being tailored to power CNTY sensors integrated into a variety of structures that could monitor damage, strain, temperature, and others.

Damage Monitoring of Braided Composites Using CNT Yarn Sensor Based on Artificial Fish Swarm Algorithm.

This study aims to enable intelligent structural health monitoring of internal damage in aerospace structural components, providing a crucial means of assuring safety and reliability in the aerospace field. To address the limitations and assumptions of traditional monitoring methods, carbon nanotube (CNT) yarn sensors are used as key elements. These sensors are woven with carbon fiber yarns using a three-dimensional six-way braiding process and cured with resin composites. To optimize the sensor configuration, an artificial fish swarm algorithm (AFSA) is introduced, simulating the foraging behavior of fish to determine the best position and number of CNT yarn sensors. Experimental simulations are conducted on 3D braided composites of varying sizes, including penetration hole damage, line damage, and folded wire-mounted damage, to analyze the changes in the resistance data of carbon nanosensors within the damaged material. The results demonstrate that the optimized configuration of CNT yarn sensors based on AFSA is suitable for damage monitoring in 3D woven composites. The experimental positioning errors range from 0.224 to 0.510 mm, with all error values being less than 1 mm, thus achieving minimum sensor coverage for a maximum area. This result not only effectively reduces the cost of the monitoring system, but also improves the accuracy and reliability of the monitoring process.

Environment-Adaptable Rotational Energy Harvesters Based on Nylon-core Coiled Carbon Nanotube Yarns.

Owing to increasing amount of research on energy harvesting, studies on harvesters for practical application and their performance are attracting attention. Therefore, studies on the use of continuous energy as an energy source for energy-harvesting devices are being conducted, and fluid flows, e.g., wind, river flow, and sea wave, are widely used as input energy sources for continuous energy harvesting. A new energy-harvesting technology has emerged based on the mechanical stretch and release of coiled carbon nanotube (CNT) yarns, which generate energy based on the change in the electrochemical double-layer capacitance. First, this CNT yarn-based mechanical energy harvester is demonstrated, which is applicable to various environments where fluid flow exists. This environment-adaptable harvester uses rotational energy as the mechanical energy source and is tested in river and ocean environments. Moreover, an attachable-type harvester for the application of the existing rotational system is devised. In the case of a slow rotational environment, a square-wave strain-applying harvester has been implemented, which can convert sinusoidal strain motion into square-wave strain motion for high output voltages. To achieve high performance of practical harvesting applications, a scale-up method for powering signal-transmitting devices has been implemented.

Stepwise Artificial Yarn Muscles with Energy-Free Catch States Driven by Aluminum-Ion Insertion.

Present artificial muscles have been suffering from poor actuation step precision and the need of energy input to maintain actuated states due to weak interactions between guest and host materials or the unstable structural changes. Herein, these challenges are addressed by deploying a mechanism of reversible faradaic insertion and extraction reactions between tetrachloroaluminate ions and collapsed carbon nanotubes. This mechanism allows tetrachloroaluminate ions as a strong but dynamic "locker" to achieve an energy-free high-tension catch state and programmable stepwise actuation in the yarn muscle. When powered off, the muscle nearly 100% maintained any achieved contractile strokes even under loads up to 96,000 times the muscle weight. The actuation mechanism allowed the programmable control of stroke steps down to 1% during reversible actuation. The isometric stress generated by the yarn muscle (14.6 MPa in maximum, 40 times that of skeletal muscles) was also energy freely lockable and step controllable with high precision. Importantly, when fully charged, the muscle stored energy with a high capacity of 102 mAh g-1, allowing the muscle as a battery to power secondary muscles or other devices.

More Powerful Twistron Carbon Nanotube Yarn Mechanical Energy Harvesters.

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.

High-Power Hydro-Actuators Fabricated from Biomimetic Carbon Nanotube Coiled Yarns with Fast Electrothermal Recovery.

Bioinspired yarn/fiber structured hydro-actuators have recently attracted significant attention. However, most water-driven mechanical actuators are unsatisfactory because of the slow recovery process and low full-time power density. A rapidly recoverable high-power hydro-actuator is reported by designing biomimetic carbon nanotube (CNT) yarns. The hydrophilic CNT (HCNT) coiled yarn was prepared by storing pre-twist into CNT sheets and subsequent electrochemical oxidation (ECO) treatment. The resulting yarn demonstrated structural stability even when one end was cut off without the possible loss of pre-stored twists. The HCNT coiled yarn actuators provided maximal contractile work of 863 J/kg at 11.8 MPa stress when driven by water. Moreover, the recovery time of electrically heated yarns at a direct current voltage of 5 V was 95% shorter than that of neat yarns without electric heating. Finally, the electrothermally recoverable hydro-actuators showed a high actuation frequency (0.17 Hz) and full-time power density (143.8 W/kg).

Enhancement of the mechanical and thermal transport properties of carbon nanotube yarns by boundary structure modulation.

Carbon nanotubes (CNTs) exhibit extremely high nanoscopic thermal/electrical transport and mechanical properties. However, the macroscopic properties of assembled CNTs are significantly lower than those of CNTs because of the boundary structure between the CNTs. Therefore, it is crucial to understand the relationship between the nanoscopic boundary structure in CNTs and the macroscopic properties of the assembled CNTs. Previous studies have shown that the nanoscopic phonon transport and macroscopic thermal transport in CNTs are improved by Joule annealing because of the improved boundary Van-der-Waals interactions between CNTs via the graphitization of amorphous carbon. In this study, we investigate the mechanical strength and thermal/electrical transport properties of CNT yarns with and without Joule annealing at various temperatures, analyzing the phenomena occurring at the boundaries of CNTs. The obtained experimental and theoretical results connect the nanoscopic boundary interaction of CNTs in CNT yarns and the macroscopic mechanical and transport properties of CNT yarns.

Twist-Stabilized, Coiled Carbon Nanotube Yarns with Enhanced Capacitance.

Coil-structured carbon nanotube (CNT) yarns have recently attracted considerable attention. However, structural instability due to heavy twist insertion, and inherent hydrophobicity restrict its wider application. We report a twist-stable and hydrophilic coiled CNT yarn produced by the facile electrochemical oxidation (ECO) method. The ECO-treated coiled CNT yarn is prepared by applying low potentiostatic voltages (3.0-4.5 V vs Ag/AgCl) between the coiled CNT yarn and a counter electrode immersed in an electrolyte for 10-30 s. Notably, a large volume expansion of the coiled CNT yarns prepared by electrochemical charge injection produces morphological changes, such as surface microbuckling and large reductions in the yarn bias angle and diameter, resulting in the twist-stability of the dried ECO-treated coiled CNT yarns with increased yarn density. The resulting yarns are well functionalized with oxygen-containing groups; they exhibit extrinsic hydrophilicity and significantly improved capacitance (approximately 17-fold). We quantitatively explain the origin of the capacitance improvement using theoretical simulations and experimental observations. Stretchable supercapacitors fabricated with the ECO-treated coiled CNT yarns show high capacitance (12.48 mF/cm and 172.93 mF/cm2, respectively) and great stretchability (80%). Moreover, the ECO-treated coiled CNT yarns are strong enough to be woven into a mask as wearable supercapacitors.

Bio-Inspired Hierarchical Carbon Nanotube Yarn with Ester Bond Cross-Linkages towards High Conductivity for Multifunctional Applications.

The cross-linked hierarchical structure in biological systems provides insight into the development of innovative material structures. Specifically, the sarcoplasmic reticulum muscle is able to transmit electrical impulses in skeletal muscle due to its cross-linked hierarchical tubular cell structure. Inspired by the cross-linked tubular cell structure, we designed and built chemical cross-links between the carbon nanotubes within the carbon nanotube yarn (CNT yarn) structure by an esterification reaction. Consequently, compared with the pristine CNT yarn, its electrical conductivity dramatically enhanced 348%, from 557 S/cm to 1950 S/cm. Furthermore, when applied with three voltages, the electro-thermal temperature of esterified CNT yarn reached 261 °C, much higher than that of pristine CNT yarn (175 °C). In addition, the esterified CNT yarn exhibits a linear and stable piezo-resistive response, with a 158% enhanced gauge factor (the ratio of electrical resistance changing to strain change ~1.9). The superconductivity, flexibility, and stable sensitivity of the esterified flexible CNT yarn demonstrate its great potential in the applications of intelligent devices, smart clothing, or other advanced composites.

Nanostructured Inorganic Chalcogenide-Carbon Nanotube Yarn having a High Thermoelectric Power Factor at Low Temperature.

As power-conversion devices, flexible thermoelectrics that enable conformal contact with heat sources of arbitrary shape are attractive. However, the low performance of flexible thermoelectric materials, which does not exceed those of brittle inorganic counterparts, hampers their practical applications. Herein, we propose inorganic chalcogenide-nanostructured carbon nanotube (CNT) yarns with outstanding power factor at a low temperature using electrochemical deposition. The inorganic chalcogenide-nanostructured CNT yarns exhibit the power factors of 3425 and 2730 µW/(m·K2) at 298 K for the p- and n-type, respectively, which is higher than those of previously reported flexible TE materials. On the basis of excellent performance and geometry advantage of the nanostructured CNT yarn for modular design, all-CNT based thermoelectric generators have been easily fabricated, showing the maximum power densities of 24 and 380 mW/m2 at ΔT = 5 and 20 K, respectively. These results provide a promising strategy for the realization of high-performance flexible thermoelectric materials and devices for flexible/or wearable self-powering systems.

Effect of Polymer Viscosity and Polymerization Kinetics on the Electrical Response of Carbon Nanotube Yarn/Vinyl Ester Monofilament Composites.

The effect of polymerization kinetics and resin viscosity on the electrical response of a single carbon nanotube yarn (CNTY) embedded in a vinyl ester resin (VER) during polymerization was investigated. To analyze the effect of the polymerization kinetics, the concentration of initiator (methyl ethyl ketone peroxide) was varied at three levels, 0.6, 0.9, and 1.2 wt.%. Styrene monomer was added to VER, to reduce the polymer viscosity and to determine its effect on the electrical response of the CNTY upon resin wetting and infiltration. Upon wetting and wicking of the CNTY by VER, a transient decrease in the CNTY electrical resistance (ca. -8%) was observed for all initiator concentrations. For longer times, this initial decrease in electrical resistance may become a monotonic decrease (up to ca. -17%) or change its trend, depending on the initiator concentration. A higher concentration of initiator showed faster and more negative electrical resistance changes, which correlate with faster gel times and higher build-up of residual stresses. An increase in styrene monomer concentration (reduced viscosity) resulted in an upward shift of the electrical resistance to less negative values. Several mechanisms, including wetting, wicking, infiltration, electronic transfer, and shrinkage, are attributed to the complex electrical response of the CNTY upon resin wetting and infiltration.

Electrical Resistance Sensing of Epoxy Curing Using an Embedded Carbon Nanotube Yarn.

Curing effects were investigated by using the electrical response of a single carbon nanotube yarn (CNTY) embedded in an epoxy resin during the polymerization process. Two epoxy resins of different viscosities and curing temperatures were investigated, varying also the concentration of the curing agent. It is shown that the kinetics of resin curing can be followed by using the electrical response of an individual CNTY embedded in the resin. The electrical resistance of an embedded CNTY increased (~ 9%) after resin curing for an epoxy resin cured at 130 °C with viscosity of ~ 59 cP at the pouring/curing temperature ("Epon 862"), while it decreased (~ -9%) for a different epoxy cured at 60 °C, whose viscosity is about double at the corresponding curing temperature. Lowering the curing temperature from 60 °C to room temperature caused slower and smoother changes of electrical resistance over time and smaller (positive) residual resistance. Increasing the concentration of the curing agent caused a faster curing kinetics and, consequently, more abrupt changes of electrical resistance over time, with negative residual electrical resistance. Therefore, the resin viscosity and curing kinetics play a paramount role in the CNTY wicking, wetting and resin infiltration processes, which ultimately govern the electrical response of the CNTY immersed into epoxy.

Carbon Nanotube Yarn Microelectrodes Promote High Temporal Measurements of Serotonin Using Fast Scan Cyclic Voltammetry.

Carbon fiber-microelectrodes (CFMEs) have been the standard for neurotransmitter detection for over forty years. However, in recent years, there have been many advances of utilizing alternative nanomaterials for neurotransmitter detection with fast scan cyclic voltammetry (FSCV). Recently, carbon nanotube (CNT) yarns have been developed as the working electrode materials for neurotransmitter sensing capabilities with fast scan cyclic voltammetry. Carbon nanotubes are ideal for neurotransmitter detection because they have higher aspect ratios enabling monoamine adsorption and lower limits of detection, faster electron transfer kinetics, and a resistance to surface fouling. Several methods to modify CFMEs with CNTs have resulted in increases in sensitivity, but have also increased noise and led to irreproducible results. In this study, we utilize commercially available CNT-yarns to make microelectrodes as enhanced neurotransmitter sensors for neurotransmitters such as serotonin. CNT-yarn microelectrodes have significantly higher sensitivities (peak oxidative currents of the cyclic voltammograms) than CFMEs and faster electron transfer kinetics as measured by peak separation (ΔEP) values. Moreover, both serotonin and dopamine are adsorption controlled to the surface of the electrode as measured by scan rate and concentration experiments. CNT yarn microelectrodes also resisted surface fouling of serotonin onto the surface of the electrode over thirty minutes and had a wave application frequency independent response to sensitivity at the surface of the electrode.

Carbon Nanotube Yarn for Fiber-Shaped Electrical Sensors, Actuators, and Energy Storage for Smart Systems.

Smart systems are those that display autonomous or collaborative functionalities, and include the ability to sense multiple inputs, to respond with appropriate operations, and to control a given situation. In certain circumstances, it is also of great interest to retain flexible, stretchable, portable, wearable, and/or implantable attributes in smart electronic systems. Among the promising candidate smart materials, carbon nanotubes (CNTs) exhibit excellent electrical and mechanical properties, and structurally fabricated CNT-based fibers and yarns with coil and twist further introduce flexible and stretchable properties. A number of notable studies have demonstrated various functions of CNT yarns, including sensors, actuators, and energy storage. In particular, CNT yarns can operate as flexible electronic sensors and electrodes to monitor strain, temperature, ionic concentration, and the concentration of target biomolecules. Moreover, a twisted CNT yarn enables strong torsional actuation, and coiled CNT yarns generate large tensile strokes as an artificial muscle. Furthermore, the reversible actuation of CNT yarns can be used as an energy harvester and, when combined with a CNT supercapacitor, has promoted the next-generation of energy storage systems. Here, progressive advances of CNT yarns in electrical sensing, actuation, and energy storage are reported, and the future challenges in smart electronic systems considered.

Spatiotemporal characteristics of neural activity in tibial nerves with carbon nanotube yarn electrodes.

BACKGROUND: Reliable interfacing with peripheral nervous system is essential to extract neural signals. Current implantable peripheral nerve electrodes cannot provide long-term reliable interfaces due to their mechanical mismatch with host nerves. Carbon nanotube (CNT) yarns possess excellent mechanical flexibility and electrical conductivity. It is of great necessity to investigate the selectivity of implantable CNT yarn electrodes. NEW METHOD: Neural interfaces were fabricated with CNT yarn electrodes insulated with Parylene-C. Acute recordings were carried out on tibial nerves of rats, and compound nerve action potentials (CNAPs) were electrically evoked by biphasic current stimulation of four toes. Spatiotemporal characteristics of neural activity and spatial selectivity of the electrodes, denoted by selectivity index (SI), were analyzed in detail. RESULTS: Conduction velocities of sensory afferent fibers recorded by CNT yarn electrodes varied between 4.25 m/s and 37.56 m/s. The SI maxima for specific toes were between 0.55 and 0.99 across seven electrodes. SIs for different CNT yarn electrodes are significantly different among varied toes. COMPARISON WITH EXISTING METHODS: Most single CNT yarn electrode with a ∼ 500 µm exposed length can be sensitive to one or two specific toes in rodent animals. While, it is only possible to discriminate two non-adjacent toes by multisite TIME electrodes. CONCLUSION: Single CNT yarn electrode exposed ∼ 500 µm showed SI values for different toes comparable to a multisite TIME electrode, and had high spatial selectivity for one or two specific toes. The electrodes with cross section exposed could intend to be more sensitive to one specific toe.

Enhancing the Work Capacity of Electrochemical Artificial Muscles by Coiling Plies of Twist-Released Carbon Nanotube Yarns.

Twisted-yarn-based artificial muscles can potentially be used in diverse applications, such as valves in microfluidic devices, smart textiles, air vehicles, and exoskeletons, because of their high torsional and tensile strokes, high work capacities, and long cycle life. Here, we demonstrate electrochemically powered, hierarchically twisted carbon nanotube yarn artificial muscles that have a contractile work capacity of 3.78 kJ/kg, which is 95 times the work capacity of mammalian skeletal muscles. This record work capacity and a tensile stroke of 15.1% were obtained by maximizing yarn capacitance by optimizing the degree of inserted twist in component yarns that are plied until fully coiled. These electrochemically driven artificial muscles can be operated in reverse as mechanical energy harvesters that need no externally applied bias. In aqueous sodium chloride electrolyte, a peak electrical output power of 0.65 W/kg of energy harvester was generated by 1 Hz sinusoidal elongation.

Flexible electrochromic materials based on CNT/PDA hybrids.

Materials that change color in response to external stimuli can cater to diverse applications from sensing to art. If made flexible, stretchable and weavable, they may even be directly integrated with advanced technologies such as smart textiles. A new class of engineered composite based on polydiacetylene (PDA) functionalized carbon nanotubes (CNT) shows tremendous potential in this regard. While the inherent multi stimuli chromatic response of the polymer (blue to red) is retained, the underlying conducting CNTs invoke electrochromism in PDA. Further, the fiber form factor of dry-spun CNT yarns facilitate direct weaving of large scale electrochromic fabrics, where current flow and thus color change can be accurately controlled. This review summarizes the fundamental aspects of CNT yarns and PDAs, focusing especially on their interaction chemistry which results in the scientifically and commercially appealing electrochromic transition in these hybrids.

Foil Strain Gauges Using Piezoresistive Carbon Nanotube Yarn: Fabrication and Calibration.

Carbon nanotube yarns are micron-scale fibers comprised by tens of thousands of carbon nanotubes in their cross section and exhibiting piezoresistive characteristics that can be tapped to sense strain. This paper presents the details of novel foil strain gauge sensor configurations comprising carbon nanotube yarn as the piezoresistive sensing element. The foil strain gauge sensors are designed using the results of parametric studies that maximize the sensitivity of the sensors to mechanical loading. The fabrication details of the strain gauge sensors that exhibit the highest sensitivity, based on the modeling results, are described including the materials and procedures used in the first prototypes. Details of the calibration of the foil strain gauge sensors are also provided and discussed in the context of their electromechanical characterization when bonded to metallic specimens. This characterization included studying their response under monotonic and cyclic mechanical loading. It was shown that these foil strain gauge sensors comprising carbon nanotube yarn are sensitive enough to capture strain and can replicate the loading and unloading cycles. It was also observed that the loading rate affects their piezoresistive response and that the gauge factors were all above one order of magnitude higher than those of typical metallic foil strain gauges. Based on these calibration results on the initial sensor configurations, new foil strain gauge configurations will be designed and fabricated, to increase the strain gauge factors even more.

Ion Beam Modification of Carbon Nanotube Yarn in Air and Vacuum.

We studied the effects ion beam irradiation on carbon nanotube (CNT) yarns. CNT yarn was fabricated by drawing and spinning CNT sheets from a vertically aligned CNT forest. The yarn was irradiated by 2.5 MeV protons in either vacuum or air. Irradiation in air was achieved by directing the proton beam through a 0.025 mm thick Ti window. Irradiation in vacuum occurred at a pressure of <10-6 torr at room temperature and at an elevated temperature of 600 °C. Tensile testing revealed that CNT yarn irradiated in air increased in tensile strength with increasing proton fluence. For yarn irradiated in vacuum, however, the strength decreased with increasing fluence. We believe that irradiation-induced excitation and trapping/bonding of gas atoms between tubes may play a role for the mechanical property changes.