The effect of multi-walled carbon nanotube pretreatments on the electrodeposition of Ni-MWCNTs coatings

Two different chemical treatments were performed on multi-walled carbon nanotubes (MWCNTs), namely functionalization, and shortening-functionalization processes. Then, nickel-MWCNTs coatings were co-electrodeposited. The results showed that the chemically shortened nanotubes were behaved as inert particles, and embedded into the nickel matrix, whilst the long functionalized nanotubes showed metallic behavior and during electrodeposition, they were incorporated into the nickel matrix. In similar plating condition, the amount of co-deposited shortened nanotubes was more than elongated ones. Furthermore, it was revealed that the pretreatment of nanotubes significantly affected the microstructure, surface morphology, hardness and corrosion resistance of deposited coatings.     

Influence of air-oxidation on electric double layer capacitances of multi-walled carbon nanotube electrodes

In this work, air-oxidized multi-walled carbon nanotube (MWCNT) electrodes have been prepared from catalytically grown MWCNTs of high purity and narrow diameter distribution. The experimental results show that air-oxidation modifies the intrinsic structure of individual MWCNTs and a little improves the dispersity of the MWCNTs. The specific capacitances of the electrodes in electric double layer capacitors (EDLCs) based on oxidized MWCNTs are obviously improved through air-oxidation. The specific capacitance of 50 F/g is obtained in the air-oxidized MWCNTs at 600 °C on a single cell device with 35 wt% H₂SO₄ as an electrolyte. This is probably increased BET specific surface area and mesopore volume of the oxidized MWCNT electrode materials of EDLCs. These properties are, therefore highly desirable for the development of electrochemical capacitors with high power and long cycle life.     

Reactor scale modeling of multi-walled carbon nanotube growth

As the mechanisms of carbon nanotube (CNT) growth becomes known, it becomes important to understand how to implement this knowledge into reactor scale models to optimize CNT growth. In past work, we have reported fundamental mechanisms and competing deposition regimes that dictate single wall carbon nanotube growth. In this study, we will further explore the growth of carbon nanotubes with multiple walls. A tube flow chemical vapor deposition reactor is simulated using the commercial software package COMSOL, and considered the growth of single- and multi-walled carbon nanotubes. It was found that the limiting reaction processes for multi-walled carbon nanotubes change at different temperatures than the single walled carbon nanotubes and it was shown that the reactions directly governing CNT growth are a limiting process over certain parameters. This work shows that the optimum conditions for CNT growth are dependent on temperature, chemical concentration, and the number of nanotube walls. Optimal reactor conditions have been identified as defined by (1) a critical inlet methane concentration that results in hydrogen abstraction limited versus hydrocarbon adsorption limited reaction kinetic regime, and (2) activation energy of reaction for a given reactor temperature and inlet methane concentration. Successful optimization of a CNT growth processes requires taking all of those variables into account.     

Comparative study on modification of multi-walled carbon nanotubes by a hydrophilic polymer with different approaches

The multi-walled carbon nanotubes (MWNTs) modified by a hydrophilic polymer were prepared with polymerization and blending approaches. The differences of both modified MWNTs were compared by Fourier transform infrared and Raman spectroscopies, thermogravimetric analysis and transmission electron microscopy. Chemical grafting reaction had occurred between MWNTs and polyvinyl pyrrolidone (PVP) after modification with polymerization and blending approaches. Polymerization modification can graft more PVP on the surface of MWNTs compared with blending modification. Polymerization modification of MWNTs belongs to the “grafting from” mechanism, while blending modification belongs to the “grafting to” mechanism. Modified MWNTs exhibit remarkable solubility in water, ethanol and dimethyl formamide.     

Thermal conductivity of multi-walled carbon nanotubes:Molecular dynamics simulations

Heat conduction in single-walled carbon nanotubes(SWCNTs) has been investigated by using various methods, while less work has been focused on multi-walled carbon nanotubes(MWCNTs). The thermal conductivities of the double-walled carbon nanotubes(DWCNTs) with two different temperature control methods are studied by using molecular dynamics(MD) simulations. One case is that the heat baths(HBs) are imposed only on the outer wall, while the other is that the HBs are imposed on both the two walls. The results show that the ratio of the thermal conductivity of DWCNTs in the first case to that in the second case is inversely proportional to the ratio of the cross-sectional area of the DWCNT to that of its outer wall. In order to interpret the results and explore the heat conduction mechanisms, the inter-wall thermal transport of DWCNTs is simulated. Analyses of the temperature profiles of a DWCNT and its two walls in the two cases and the interwall thermal resistance show that in the first case heat is almost transported only along the outer wall, while in the second case a DWCNT behaves like parallel heat transport channels in which heat is transported along each wall independently.This gives a good explanation of our results and presents the heat conduction mechanisms of MWCNTs.     

Functional multi-walled carbon nanotube/polysiloxane composite films as supports of PtNi alloy nanoparticles for methanol electro-oxidation

We demonstrate the use of molecular monolayers to enhance the nucleation of electrocatalytically active PtNi alloy nanoparticles onto the multi-walled carbon nanotubes (MWCNTs). After the siloxane was polymerized on the nanotube surfaces, the carbon nanotubes were embedded within the polysiloxane shell with a hydrophilic amino group situated outside. Subsequent deposition of PtNi nanoparticles led to high density of 3-10 nm diameter PtNi alloy nanoparticles uniformly deposited along the length of the carbon nanotubes. The presence of MWCNTs and PtNi in the composite films was confirmed by transmission electron microscopy (TEM), X-ray diffraction (XRD) and energy dispersion X-ray spectra analysis (EDS). The electrocatalytic activity of the PtNi-modified MWCNT/polysiloxane (PtNi/Si-MWCNT) composite electrode for electro-oxidation of methanol was investigated by cyclic voltammetry (CV), and excellent electrocatalytic activity can be observed.     

Surface modification of multi-walled carbon nanotubes by O2 plasma

The surface modification of multi-walled carbon nanotubes (MWCNTs) by O₂ plasma was carried out in this study. In order to achieve a relatively homogeneous treatment of MWCNTs powder, a rotating barrel fixed between the two discharge electrodes was used. The effect of plasma treatment parameters, such as power, time, and positions of samples (inside and outside the barrel), on the morphology and structure of MWCNTs surface was systematically analyzed by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). The results showed that the direct discharge (outside the barrel) could result in not only a quick grafting of polar functional groups but also an easy damage of MWCNTs after longer time, particularly under intensive power. It was found that the surface of MWCNTs powder might be changed in three steps—expansion (loosed structure formed), peel off and oxidization with increasing of treatment time during the irradiation. In this way, a complete purification of MWCNTs powder could be finished within 30 min via plasma treatment. Our work suggested that plasma treatment could be a simple and nonpolluting method for a large scale purification of MWCNTs.     

Comparative study of electrochemical capacitance of multi-walled carbon nanotubes before and after chopping

In the work, short multi-walled carbon nanotubes (S-CNTs) were synthesized by chopping conventional μm-long multi-walled carbon nanotubes (L-CNTs) under ultrasonication in H₂SO₄/HNO₃ mixed acids. A comparative electrochemical investigation performed in 6 M KOH solution demonstrated that a specific capacitance (SC) of ca. 14.6 μF cm⁻² was delivered by the S-CNTs with the specific surface area (SSA) of 207 m² g⁻¹, much larger than that of ca. 10.1 μF cm⁻² for the L-CNTs with the SSA of 223 m² g⁻¹, the reason for which was that S-CNTs with two open ends, due to good ion penetrability, provided more entrances for electrolyte ions to access the inner surface easily through their shorter inner pathway so as to enhance their SSA utilization and geometric SC. The surface structure disruption of S-CNTs, owing to ultrasonication and oxidation during chopping process, deteriorated their electronic conductivity and resulted in an inferior power property in contrast to L-CNTs.     

Mild hydrothermal treatment to prepare highly dispersed multi-walled carbon nanotubes

Multi-walled carbon nanotubes (MWCNTs) with improved dispersion property have been prepared by a mild and fast hydrothermal treatment. The hydrothermal process avoids using harsh oxidants and organic solvents, which is environmental friendly and greatly decreases the damage to intrinsic structure of MWCNTs. The modified MWCNTs were highly soluble in polar solvents such as water, ethanol and dimethylformamide. Morphological observation by TEM indicated that the diameter and inherent structure were well reserved in modified MWCNTs. X-ray photoelectron spectroscopy and Raman spectroscopy were used to quantify functional groups created on the MWCNT surface, and to determine rational parameters of hydrothermal process.     

Effect of oxyfluorination on gas sensing behavior of polyaniline-coated multi-walled carbon nanotubes

Polyaniline-coated multi-walled carbon nanotubes were prepared by in situ chemical polymerization method for the novel sensing materials of ammonia gas. The thickness of the polyaniline coatings was controlled by the oxyfluorination treatment on the multi-walled carbon nanotubes. The oxyfluorination with higher oxygen content produced the more hydrophilic functional groups on the surface of multi-walled carbon nanotubes. Both the resistivity change and the response time were significantly improved with high repeatability using the more hydrophilic multi-walled carbon nanotubes which were modified with oxyfluorination.     

Photoresponsive conductance switching of multi-walled carbon nanotubes bearing covalently linked spironaphthoxazine

Multi-walled carbon nanotubes functionalized with a photochromic spironaphthoxazines (MWCNTs-SPO) were synthesized by the reaction between the hydroxyl group of SPO and the carbonyl chloride groups on the surface of MWCNTs. The functional spirooxazine photochromic groups on the surface of MWCNTs were identified by the X-ray photoelectron spectroscopy. As a novel derivative of MWCNTs, photoresponsive conductance switching of the MWCNTs-SPO was demonstrated under a 365 nm UV light irradiation. A simple photoinduced resistance measurement following the cyclic irradiation of UV light shows a very reversible response. The effect of the electron injection in the SPO is rationalized in terms of the HOMO–LUMO energy levels of both spiro and merocyanine forms.     

Effects of corona discharge on the surface structure, morphology and properties of multi-walled carbon nanotubes

Multi-walled carbon nanotubes (MWCNTs) were modified by corona discharge and then heat treated in the air. The influences of corona discharge parameters such as treatment time and processing power were investigated. The results of energy dispersive X-ray analysis (EDX) and thermogravimetric analysis (TGA) indicated the introduction of oxygen-containing functional groups onto the surface of the MWCNTs after heat treatment. The water contact angle tests showed that the hydrophobicity of the MWCNTs was decreased to some extent. The static water contact angle was reduced from 146° to 122° when the time of the corona discharge treatment reached 3 min at the processing power of 200 W. The enhanced thermomechanical and mechanical properties of epoxy nanocomposites filled with the corona discharge treated MWCNTs were observed. The modified MWCNTs conferred better properties on the composites than the pristine MWCNTs because of the improved dispersion of MWCNTs in matrix and the enhanced interfacial interaction between the treated MWCNTs and epoxy.     

Thermal and electrical conductivity of poly(l-lactide)/multiwalled carbon nanotube nanocomposites

Multiwalled carbon nanotubes (MWCNTs) are considered to be the ideal reinforcing agent for high-strength polymer composites, because of their fantastic mechanical strength, high electrical and thermal conductivity and high aspect ratio. Polymer/MWCNTs composites are easily molded, and the resulting shaped plastic articles have a perfect surface appearance compared with polymer composites made using usual carbon or glass fibers. Good interfacial adhesion between the MWCNTs and the polymer matrix is essential for efficient load transfer in the composite. The ultrahigh strength polymer composites demand the uniform dispersion of the MWCNTs in the polymer matrix without their aggregation and the good miscibility between MWCNT and polymer matrix. This approach can also be applied to biodegradable synthetic aliphatic polyesters such as poly(l-lactide) (PLLA), which has received a great deal of attention due to environmental concerns. In this study, PLLA was melt-compounded with MWCNTs. A high degree of dispersion of the MWCNTs in the composites was obtained by grafting PLLA onto the MWCNTs (PLLA-g-MWCNTs). After oxidizing the MWCNTs by treating them with strong acids, they were reacted with l-lactide to produce the PLLA-g-MWCNTs. The mechanical properties of the PLLA/PLLA-g-MWCNT composite were higher than those of the PLLA/MWCNT composite. The electrical conductivity of the composites was determined by measuring the volume resistivity, which is a value of the resistance expressed in a unit volume by two-probe method. The thermal diffusivity and heat capacity of composites was measured by laser flash method, and the effects of modification of the MWCNT in PLLA matrix are discussed.     

Electrochemical and surface characterisation of gold nanoparticle decorated multi-walled carbon nanotubes

A novel type of gold nanoparticle/multi-walled carbon nanotube (AuNP/MWCNT) composite electrodes is presented. The electrochemical reduction of oxygen on these hybrid electrodes was studied using the rotating disk electrode (RDE) method. The AuNP/MWCNT nanocomposites were prepared by sputter deposition of gold in argon atmosphere on MWCNTs followed by heat-treatment of the catalyst at different temperatures. High-resolution scanning electron microscopy (HR-SEM), glancing incidence angle X-ray powder diffraction (GIXRD) and small-angle X-ray scattering (SAXS) techniques were employed to characterise the surface structure and morphology of catalyst materials. Au nanoparticles with diameter around 20 nm were dispersed at the tips and on the sidewalls of nanotubes. Electrochemical measurements were performed to demonstrate the electrocatalytic properties of the composite catalysts towards O₂ reduction in acid media. The successful preparation of AuNP/MWCNT nanocomposites by magnetron sputtering opens up the possibility of making an efficient dispersion of nanoparticles for electrocatalyst design.     

The effect of chemical treatment on the crystallinity of multi-walled carbon nanotubes

Multi-walled carbon nanotubes (MWCNTs) were chemically treated using nitric acid solution for different time. Quantitative analysis of the crystallinity of the MWCNTs was performed by wide-angle X-ray diffraction (WAXD). The WAXD patterns were deconvoluted into the crystalline diffraction peaks and the amorphous scattering peaks. The introduction of a correction factor for the integrated peak intensity can enhance the computational accuracy of the crystallinity. With increasing the chemical treatment time, the crystallinity of MWCNTs first increases, and then decreases. When the chemical treatment time is equal to 2 h, the crystallinity of MWCNTs reaches the maximum of 85.9%. Moreover, the degree of order in the structures of chemically treated MWCNTs was further studied by thermogravimetric analysis (TGA) and high-resolution transmission electron microscopy (HRTEM). It was found that the external walls of chemically treated MWCNTs with high crystallinity consist of a series of perfectly continuous and straight graphite layers.     

Improving the surface properties of multi-walled carbon nanotubes after irradiation with gamma rays

The effects of gamma-irradiation on the modification of the surface and structure of multi-walled carbon nanotubes were studied. Gamma-irradiation affected the graphitization properties of functional groups, and decreased the diameter of multi-walled carbon nanotubes. The irradiated multi-walled carbon nanotubes with the absorbed dose of 100 kGy exhibited a larger specific surface area and microporous volume as compared with the other samples. The Raman spectroscopy and X-ray photoelectron spectroscopy showed that the interaction between the gamma-irradiation and the multi-walled carbon nanotubes with the absorbed dose of 150 kGy destroyed the nanostructure of carbons, leading to the formation of diamond-like structures and carbon oxides. In addition, gamma-irradiation with the absorbed dose of 100 kGy improved multi-walled carbon nanotubes graphitization and surface properties while at higher absorbed dose (150 kGy), it induced damaged structures (sp³ bonds and oxygen compositions).     

Influence of the electrical field applied during thermal cycling on the conductivity of LLDPE/CNT composites

The effect of the electrical field on the conductivity of linear low-density polyethylene/carbon nanotubes/ (LLDPE/CNT) composites during temperature cycling has been investigated. Under applied voltage a positive resistivity temperature coefficient was observed during heating already at low (2–3 wt%) CNT content, followed by a large negative temperature coefficient during cooling whose value depends on the applied voltage. The resistivity values after thermal cycling were markedly lower, while they slightly increased in the absence of an electrical field. The effects of thermal cycling on structural and physical properties of the composites have been evaluated by X-ray diffraction and differential scanning calorimetry.     

MeV carbon ion irradiation-induced changes in the electrical conductivity of silver nanowire networks

MeV carbon ion irradiation-induced changes in the electrical conductivity of Silver nanowire (Ag-NW) networks is demonstrated systematically at different C⁺ ion fluences ranging from 1 × 10¹² to 1 × 10¹⁶ ions/cm² at room temperature. At low C⁺ ion fluences, the electrical conductivity of Ag-NWs decreases and subsequently increases with increase fluence. Finally, at high C⁺ ion fluences, conductivity again decreases. The variation in the electrical conductivity of Ag NW network is discussed after analysis using scanning electron microscopy (SEM) and X-ray diffraction (XRD) techniques. The observed increase in electrical conductivity is thought to be due to ion induced coalescence of Ag-NWs at contact position, which causes reduction of wire–wire contact resistance, while the decrease in electrical conductivity may be due to defect production by C⁺ ions into Ag-NWs. Ion beam technology is therefore a very promising technology that is capable of fabricating highly conductive Ag-NW networks for transparent electrodes. Moreover, a method for thinning, slicing and cutting of Ag-NWs using ion beam technology is also reported.     

Mineralization of surfactant functionalized multi-walled carbon nanotubes (MWNTs) to prepare hydroxyapatite/MWNTs nanohybrid

Multi-walled carbon nanotubes (MWNTs) were well dispersed in water and functionalized by adding surface active agent (i.e., sodium dodecyl sulfate, SDS). Subsequently, biomimetic mineralization was carried out on the SDS functionalized MWNTs by using an alternate soaking process (ASP) in the Ca/P solutions. As-prepared samples were characterized by transmission electron microscope, infrared spectrum and X-ray diffraction. The results show that nano-HA crystals were formed on the SDS functionalized MWNTs and the mineralized MWNTs remained a dispersing state. As-prepared HA-MWNTs nanohybrid combining the osteconductive property of HA and the excellent mechanical property of MWNTs will provide a promising material for bone tissue engineering.     

Effects on the field emission properties by variation in surface morphology of patterned photosensitive carbon nanotube paste using organic solvent

Photosensitive carbon nanotube (CNT) paste was prepared by 3-roll milling of multi-walled carbon nanotubes (MWNTs), UV-sensitive binder solution, and Ag as filler additives. Arrays of MWNT dots with a diode structure were fabricated by a combination of screen printing method and photolithography using these paste, and acetone utilized as the developer. The MWNT dots were well-defined and the organic binder materials in the dots were partially removed. The MWNT film without a heat treatment showed a high current density of 1.35 mA/cm² at 3.25 V/μm and low turn-on field of 2.2 V/μm at 100 μA/cm². Acetone can be used as an efficient developer to form patterns and to remove the organic residues in patterns, simultaneously.