Turning refuse plastic into multi-walled carbon nanotube forest

Abstract

A novel and effective method was devised for synthesizing a vertically aligned carbon nanotube (CNT) forest on a substrate using waste plastic obtained from commercially available water bottles. The advantages of the proposed method are the speed of processing and the use of waste as a raw material. A mechanism for the CNT growth was also proposed. The growth rate of the CNT forest was ～2.5 μm min^?1. Transmission electron microscopy images indicated that the outer diameters of the CNTs were 20–30 nm on average. The intensity ratio of the G and D Raman bands was 1.27 for the vertically aligned CNT forest. The Raman spectrum showed that the wall graphitization of the CNTs, synthesized via the proposed method was slightly higher than that of commercially available multi-walled carbon nanotubes (MWCNTs). We expect that the proposed method can be easily adapted to the disposal of other refuse materials and applied to MWCNT production industries.     

Synthesis and characterization of vertically aligned carbon nanotube forest for solid state fiber spinning

Continuous carbon nanotubes (CNT) fibers were directly spun from a vertically aligned CNT forest grown by a plasma-enhanced chemical vapor deposition (PECVD) process. The correlation of the CNT structure with Fe catalyst coarsening, reaction time, and the CNTs bundling phenomenon was investigated. We controlled the diameters and walls of the CNTs and minimized the amorphous carbon deposition on the CNTs for favorable bundling and spinning of the CNT fibers. The CNT fibers were fabricated with an as-grown vertically aligned CNT forest by a PECVD process using nanocatalyst an Al2O3 buffer layer, followed by a dry spinning process. Well-aligned CNT fibers were successfully manufactured using a dry spinning process and a surface tension-based densification process by ethanol. The mechanical properties were characterized for the CNT fibers spun from different lengths of a vertically aligned CNT forest. Highly oriented CNT fibers from the dry spinning process were characterized with high strength, high modulus, and high electrical as well as thermal conductivities for possible application as ultralight, highly strong structural materials. Examples of structural materials include space elevator cables, artificial muscle, and armor material, while multifunctional materials include E-textile, touch panels, biosensors, and super capacitors.     

Decoupled Control of Carbon Nanotube Forest Density and Diameter by Continuous‐Feed Convective Assembly of Catalyst Particles

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.     

Flow-dependent directional growth of carbon nanotube forests by chemical vapor deposition

We demonstrated that the structural formation of vertically aligned carbon nanotube (CNT) forests is primarily affected by the geometry-related gas flow, leading to the change of growth directions during the chemical vapor deposition (CVD) process. By varying the growing time, flow rate, and direction of the carrier gas, the structures and the formation mechanisms of the vertically aligned CNT forests were carefully investigated. The growth directions of CNTs are found to be highly dependent on the nonlinear local gas flows induced by microchannels. The angle of growth significantly changes with increasing gas flows perpendicular to the microchannel, while the parallel gas flow shows almost no effect. A computational fluid dynamics (CFD) model was employed to explain the flow-dependent growth of CNT forests, revealing that the variation of the local pressure induced by microchannels is an important parameter determining the directionality of the CNT growth. We expect that the present method and analyses would provide useful information to control the micro- and macrostructures of vertically aligned CNTs for various structural/electrical applications.     

Catalytic-free growth of VACNTs for energy harvesting

Abstract

The present study introduces a process to grow micro-honeycomb (µ-HC) vertically aligned carbon nanotubes (VACNTs) using thermal chemical vapor deposition technique. Methane is used as a source of carbon and hydrogen gas as a reducing agent. Where, the fabricated µ-HC structure reported in literature involves complex synthesis process and requires a catalyst layer, the novelty of the process used here lies in the fact that no catalyst layer is used for the growth of CNT network, rather copper foil is used as a substrate. The in-situ cracking of CNTs due to water treatment leads to the formation of µ-HC CNT network, which is confirmed by Raman spectroscopy. Further scanning electron microscopy analysis shows that the length of developed µ-HC CNT is ～5?µm. Hexagonal µ-HC network shows more than 94% absorption in UV-Vis-NIR wavelength region. The designed process provides high-yield with a low-cost synthesis of vertically aligned CNTs having 3?D microarchitecture. The fabricated CNT network can be used as an electrode for supercapacitor, as an active layer in a photovoltaic cell and most of the energy harvesting devices.     

Field emission characteristics from tapered ZnO nanostructures grown onto vertically aligned carbon nanotubes

Zinc oxide (ZnO) nanostructures were grown on vertically aligned carbon nanotubes (CNTs) using thermal chemical vapor deposition (CVD) to enhance the field emission characteristics. The shape of ZnO nanostructure was tapered. Scanning electron microscopy (SEM) image showed the ZnO nanostructures were grown onto CNT surface uniformly. The field electron emission of pristine CNTs and ZnO-coated CNTs were measured. The results showed that ZnO nanostructures grown onto CNTs could improve the field emission characteristics. The ZnO-coated CNTs had a threshold electric field at about 3.1 V/μm at 1.0 mA/cm². The results demonstrated that the ZnO-coated CNT is an ideal field emitter candidate material. The stability of the field emission current was also tested.     

Effects of CNT diameter on mechanical properties of aligned CNT sheets and composites

Drawing, winding, and pressing techniques were used to produce horizontally aligned carbon nanotube (CNT) sheets from free-standing vertically aligned CNT arrays. The aligned CNT sheets were used to develop aligned CNT/epoxy composites through hot-melt prepreg processing with a vacuum-assisted system. Effects of CNT diameter change on the mechanical properties of aligned CNT sheets and their composites were examined. The reduction of the CNT diameter considerably increased the mechanical properties of the aligned CNT sheets and their composites. The decrease of the CNT diameter along with pressing CNT sheets drastically enhanced the mechanical properties of the CNT sheets and CNT/epoxy composites. Raman spectra measurements showed improvement of the CNT alignment in the pressed CNT/epoxy composites. Research results suggest that aligned CNT/epoxy composites with high strength and stiffness are producible using aligned CNT sheets with smaller-diameter CNTs.     

Growth control of carbon nanotubes by plasma enhanced chemical vapor deposition

Plasma enhanced chemical vapor deposition (PECVD), which enables growth of vertically aligned carbon nanotubes (CNTs) directly onto a solid substrate, is considered to be a suitable method for preparing CNTs for nanoelectronics applications such as electron sources for field emission displays (FEDs). For these purposes, establishment of an efficient CNT growth process has been required. We have examined growth characteristics of CNTs using a radio frequency PECVD (RF-PECVD) method with the intention to develop a high efficiency process for CNT growth at a low enough temperature suitable for nanoelectronics applications. Here we report an effect of pretreatment of the catalyst thin film that plays an important role in CNT growth using RF-PECVD. Results of this study show that uniform formation of fine catalyst nanoparticles on the substrate is important for the efficient CNT growth.     

Effect of density variation and non-covalent functionalization on the compressive behavior of carbon nanotube arrays

Arrays of aligned carbon nanotubes (CNTs) have been proposed for different applications, including electrochemical energy storage and shock-absorbing materials. Understanding their mechanical response, in relation to their structural characteristics, is important for tailoring the synthesis method to the different operational conditions of the material. In this paper, we grow vertically aligned CNT arrays using a thermal chemical vapor deposition system, and we study the effects of precursor flow on the structural and mechanical properties of the CNT arrays. We show that the CNT growth process is inhomogeneous along the direction of the precursor flow, resulting in varying bulk density at different points on the growth substrate. We also study the effects of non-covalent functionalization of the CNTs after growth, using surfactant and nanoparticles, to vary the effective bulk density and structural arrangement of the arrays. We find that the stiffness and peak stress of the materials increase approximately linearly with increasing bulk density.     

Flexible High‐Conductivity Carbon‐Nanotube Interconnects Made by Rolling and Printing

Applications of carbon nanotubes (CNTs) in flexible and complementary metal‐oxide‐semiconductor (CMOS)‐based electronic and energy devices are impeded due to typically low CNT areal densities, growth temperatures that are incompatible with device substrates, and challenges in large‐area alignment and interconnection. A scalable method for continuous fabrication and transfer printing of dense horizontally aligned CNT (HA‐CNT) ribbon interconnects is presented. The process combines vertically aligned CNT (VA‐CNT) growth by thermal chemical vapor deposition, a novel mechanical rolling process to transform the VA‐CNTs to HA‐CNTs, and adhesion‐controlled transfer printing without needing a carrier film. The rolling force determines the HA‐CNT packing fraction and the HA‐CNTs are processed by conventional lithography. An electrical resistivity of 2 mΩ · cm is measured for ribbons having 800‐nm thickness, while the resistivity of copper is 100 times lower, a value that exceeds most CNT assemblies made to date, and significant improvements can be made in CNT structural quality. This rolling and printing process could be scaled to full wafer areas and more complex architectures such as continuous CNT sheets and multidirectional patterns could be achieved by straightforward design of the CNT growth process and/or multiple rolling and printing sequences.     

Transferring vertically aligned carbon nanotubes onto a polymeric substrate using a hot embossing technique for microfluidic applications

We explored the hot embossing method for transferring vertically aligned carbon nanotubes (CNTs) into microfluidic channels, fabricated on poly-methyl-methacrylate (PMMA). Patterned and unpatterned CNTs were synthesized by microwave plasma-enhanced chemical vapour deposition on silicon to work as a stamp. For hot embossing, 115°C and 1 kN force for 2 min were found to be the most suitable parameters for the complete transfer of aligned CNTs on the PMMA microchannel. Raman and SEM studies were used to analyse the microstructure of CNTs before and after hot embossing. The PMMA microparticles with dimensions (approx. 10 µm in diameter) similar to red blood cells were successfully filtered using laminar flow through these microfluidic channels. Finally, a microfluidic-based point-of-care device for blood filtration and detection of bio-molecules is drawn schematically.     

Synthesis of regular nano-pitched carbon nanotube array by using nanosphere lithography for interconnect applications

In this paper, we report a method based on nanosphere lithography technology for the synthesis of nano-pitched vertically aligned multi-walled carbon nanotube array. A monolayer of polystyrene nanospheres with diameter of 650 nm was coated on silicon oxide layer to create hexagonally arranged patterns. A metal layer, which acted as a catalyst for carbon nanotube growth, was deposited on the patterns by e-beam evaporation method. Nano-sized metallic patterns were formed by removing the polystyrene nanospheres. Uniform CNT arrays with pitch of 800 nm were successfully synthesized from the metallic patterns by plasma enhanced chemical vapor deposition. Using nanosphere lithography, the pitch of the single CNT array can be well-controlled. Therefore, the as-grown CNTs have potential applications in advanced interconnects technology and other nano applications.     

Effects of vertically aligned carbon nanotubes on shear performance of laminated nanocomposite bonded joints

Abstract

The main objective is to improve the most commonly addressed weakness of the laminated composites (i.e. delamination due to poor interlaminar strength) using carbon nanotubes (CNTs) as reinforcement between the laminae and in the transverse direction. In this work, a chemical vapor deposition technique has been used to grow dense vertically aligned arrays of CNTs over the surface of chemically treated two-dimensionally woven cloth and fiber tows. The nanoforest-like fabrics can be used to fabricate three-dimensionally reinforced laminated nanocomposites. The presence of CNTs aligned normal to the layers and in-between the layers of laminated composites is expected to considerably enhance the properties of the laminates. To demonstrate the effectiveness of our approach, composite single lap-joint specimens were fabricated for interlaminar shear strength testing. It was observed that the single lap-joints with through-the-thickness CNT reinforcement can carry considerably higher shear stresses and strains. Close examination of the test specimens showed that the failure of samples with CNT nanoforests was completely cohesive, while the samples without CNT reinforcement failed adhesively. This concludes that the adhesion of adjacent carbon fabric layers can be considerably improved owing to the presence of vertically aligned arrays of CNT nanoforests.     

Machining carbon nanotubes into uniform slices

Shearing the carbon nanotubes (CNTs) to desired size or trimming the CNT tips conveniently is usually necessary for many applications. CNTs are normally believed possessing very high strength and toughness. In this paper we present a simple and novel method to actualize this process. In this method, aligned CNT arrays were embedded in paraffin matrix, and then the materials were carefully sliced up along the direction normal to the CNTs with a microtome. These slices consisted of vertically aligned CNTs with desired and uniform length. The experiments proved that there were enough interaction forces between the CNTs and the paraffin matrix to prevent the CNTs from being pulled out during the machining process. These sheared CNTs have shown better performance for thermal interface materials and field emission applications. This process may redound to unlocking the great potential of CNT applications.     

Electrochemical properties and myocyte interaction of carbon nanotube microelectrodes

Arrays of carbon nanotube (CNT) microelectrodes (nominal geometric surface areas 20-200 μm(2)) were fabricated by photolithography with chemical vapor deposition of randomly oriented CNTs. Raman spectroscopy showed strong peak intensities in both G and D bands (G/D = 0.86), indicative of significant disorder in the graphitic layers of the randomly oriented CNTs. The impedance spectra of gold and CNT microelectrodes were compared using equivalent circuit models. Compared to planar gold surfaces, pristine nanotubes lowered the overall electrode impedance at 1 kHz by 75%, while nanotubes treated in O(2) plasma reduced the impedance by 95%. Cyclic voltammetry in potassium ferricyanide showed potential peak separations of 133 and 198 mV for gold and carbon nanotube electrodes, respectively. The interaction of cultured cardiac myocytes with randomly oriented and vertically aligned CNTs was investigated by the sectioning of myocytes using focused-ion-beam milling. Vertically aligned nanotubes deposited by plasma-enhanced chemical vapor deposition (PECVD) were observed to penetrate the membrane of neonatal-rat ventricular myocytes, while randomly oriented CNTs remained external to the cells. These results demonstrated that CNT electrodes can be leveraged to reduce impedance and enhance biological interfaces for microelectrodes of subcellular size.     

Non-destructive characterization of structural hierarchy within aligned carbon nanotube assemblies

Understanding and controlling the hierarchical self-assembly of carbon nanotubes (CNTs) is vital for designing materials such as transparent conductors, chemical sensors, high-performance composites, and microelectronic interconnects. In particular, many applications require high-density CNT assemblies that cannot currently be made directly by low-density CNT growth, and therefore require post-processing by methods such as elastocapillary densification. We characterize the hierarchical structure of pristine and densified vertically aligned multi-wall CNT forests, by combining small-angle and ultra-small-angle x-ray scattering (USAXS) techniques. This enables the nondestructive measurement of both the individual CNT diameter and CNT bundle diameter within CNT forests, which are otherwise quantified only by delicate and often destructive microscopy techniques. Our measurements show that multi-wall CNT forests grown by chemical vapor deposition consist of isolated and bundled CNTs, with an average bundle diameter of 16 nm. After capillary densification of the CNT forest, USAXS reveals bundles with a diameter >4 μm, in addition to the small bundles observed in the as-grown forests. Combining these characterization methods with new CNT processing methods could enable the engineering of macro-scale CNT assemblies that exhibit significantly improved bulk properties.     

Process intensification by CO2 for high quality carbon nanotube forest growth: Double-walled carbon nanotube convexity or single-walled carbon nanotube bowls?

Introduction of CO₂ is a facile way to tune the growth of vertically aligned double- or single-walled carbon nanotube (CNT) forests on wafers. In the absence of CO₂, a double-walled CNT convexity was obtained. With increasing concentration of CO₂, the morphologies of the forests transformed first into radial blocks, and finally into bowl-shaped forests. Furthermore, the wall number and diameter distribution of the CNTs were also modulated by varying the amount of CO₂. With increasing CO₂ concentration, CNTs with fewer wall number and smaller diameter were obtained. The addition of CO₂ is speculated to generate water and serve as a weak oxidant for high quality CNT growth. It can tune the growth rate and the morphologies of the forests, prevent the formation of amorphous carbon, and reduce the wall number of the CNTs.     

Synthesis of Well-Crystalline Lattice Carbon Nanotubes via Neutralized Cooling Method

In this contribution, vertically aligned carbon nanotubes were synthesized by chemical vapor deposition (CVD). The effects of intrinsic disorders constructed by mobile surface contaminants on the structural perfection of carbon nanotubes (CNTs) were investigated. The results indicated a complete picture on the effect of the involved parameters on the lattice defects of modulated CNTs based on the cooling step. Raman scattering showed that the different cooling methods of the CVD preforms altered the bound complex defects of the structure of the CNTs. Moreover, an array of CNTs was removed from the silicon substrate by applying the neutralized cooling method on the CVD, while the vertical and parallel orientations were retained. The FESEM images, coupled with Raman spectroscopy results, confirm the morphological improvements of the growth CNTs based on the neutralized cooling method.     

Controlled partial embedding of carbon nanotubes within flexible transparent layers

Applications of carbon nanotubes (CNTs) like field emission displays, super-capacitors, and cell growth scaffolds can benefit from controllable embedding of the CNTs in a material such that the CNTs are anchored and protrude a desired length. We demonstrate a simple method for anchoring densely packed, vertically aligned arrays of CNTs into silicone layers using spin-coating, CNT insertion, curing, and growth substrate removal. CNT arrays of 51 and 120?μm in height are anchored into silicone layers of thickness 26 and 36?μm, respectively. Scanning electron microscopy (SEM) and optical microscopy are used to characterize the sample morphology, a 5.5?m?s(-1) impinging water jet is used to apply shear stress, and a tensile test shows that the silicone layer detaches from the substrate before the CNTs are ripped from the layer. The CNTs are thus well anchored in the silicone layers. The spin-coating process gives control over layer thickness, and the method should have general applicability to various nanostructures and anchoring materials.     

Force output, control of film structure, and microscale shape transfer by carbon nanotube growth under mechanical pressure

We demonstrate that a film of vertically aligned multiwall carbon nanotubes (CNTs) can exert mechanical energy as it grows, and in our experiments the average force output is approximately 0.16 nN per CNT, for CNTs having an outer diameter of 9 nm and five walls. The film thickness after a fixed growth time and the alignment of CNTs within the film decrease concomitantly with increasing pressure which is applied by placing a weight on the catalyst substrate prior to growth, and CNTs grown under applied pressure exhibit significant structural faults. The measured mechanical energy density of CNT growth is significantly less than the energies of primary steps in the CNT formation process yet, based on the film volume, is comparable to the energy density of muscle and based on the volume of CNTs is comparable to hydraulic actuators. We utilize this principle to fabricate three-dimensional structures of CNTs which conform to the shape of a microfabricated template. This technique is a catalytic analogue to micromolding of polymer and metal microstructures; it enables growth of nanostructures in arbitrarily shaped forms having sloped surfaces and nonorthogonal corners and does not require patterning of the catalyst before growth.