Growth of multiwalled carbon nanotube arrays by chemical vapour deposition over iron catalyst and the effect of growth parameters

Multiwalled carbon nanotube (CNT) arrays were grown by catalytic thermal decomposition of acetylene, over Fe-catalyst deposited on Si-wafer in the temperature range 700-750 °C. The growth parameters were optimized to obtain dense arrays of multiwalled CNTs of uniform diameter. The vertical cross-section of the grown nanotube arrays reveals a quasi-vertical alignment of the nanotubes. The effect of varying the thickness of the catalyst layer and the effect of increasing the growth duration on the morphology and distribution of the grown nanotubes were studied. A scotch-tape test to check the strength of adhesion of the grown CNTs to the Si-substrate surface reveals a strong adhesion between the grown nanotubes and the substrate surface. Transmission electron microscopy analysis of the grown CNTs shows that the grown CNTs are multiwalled nanotubes with a bamboo structure, and follow the base-growth mechanism.     

Coupled process of plastics pyrolysis and chemical vapor deposition for controllable synthesis of vertically aligned carbon nanotube arrays

Efficient conversion of waste plastics into advanced materials is of conspicuous environmental, social and economic benefits. A coupled process of plastic pyrolysis and chemical vapor deposition for vertically aligned carbon nanotube (CNT) array growth was proposed. Various kinds of plastics, such as polypropylene, polyethylene, and polyvinyl chloride, were used as carbon sources for the controllable growth of CNT arrays. The relationship between the length of CNT arrays and the growth time was investigated. It was found that the length of aligned CNTs increased with prolonged growth time. CNT arrays with a length of 500 μm were obtained for a 40-min growth and the average growth rate was estimated to be 12 μm/min. The diameter of CNTs in the arrays can be modulated by controlling the growth temperature and the feeding rate of ferrocene. In addition, substrates with larger specific surface area such as ceramic spheres, quartz fibers, and quartz particles, were adopted to support the growth of CNT arrays. Those results provide strong evidence for the feasibility of conversion from waste plastics into CNT arrays via this reported sustainable materials processing.     

Structural and morphological dependence of carbon nanotube arrays on catalyst aggregation

Catalyst aggregation affects the growth of carbon nanotube (CNT) arrays in terms of tubular structures, waviness, entanglement, lengths, and growth density etc., which are important issues for application developments. We present a systematic correlation between the aggregation of catalyst on the SiO₂/Si substrate and the structure and morphology of CNT arrays. The thickness of the catalyst film has a direct effect on the areal density of the catalytic particles and then the alignment of the CNT array. Introducing alumina as buffer layer and annealing the catalyst film at low pressure are two effective approaches to downsize the catalyst particles and then the diameter, wall number of the CNTs. Both the size and areal density of the catalyst also change with the CNT growth in accordance with Ostwald ripening process, with the bottom of the CNT array varying from well-aligned to disordered and adhesion between catalyst particles and the substrate getting enhanced. Strategies including tuning the thickness of the catalyst film, changing buffer layer, controlling on the growth time and the system pressure were used to regulate the aggregation of the catalyst. CNT arrays from disordered to well-aligned, from multi-walled to few-walled and further to single-walled were reproducibly synthesized by chemical vapor deposition of acetylene.     

Modulating the diameter of carbon nanotubes in array form via floating catalyst chemical vapor deposition

Based on the analysis of catalyst particle formation and carbon nanotube (CNT) array growth process in floating catalyst chemical vapor deposition (CVD), delicately controlled gaseous carbon sources and catalyst precursors were introduced into the reactor for the controllable growth of CNT array. The low feeding rate of ferrocene was realized through low-temperature sublimation. With less ferrocene introduced into the reactor, the collision among the in situ formed iron atoms decreased, which led to the formation of smaller catalyst particles. The mean diameter of the CNT array, grown at 800^oC, decreased from 41 to 31 nm when the ferrocene-sublimed temperature reduced from 80 to 60^oC. Furthermore, low growth temperature was adopted in synthesis, through the modulation of the CNT diameter, by controlling the sintering of catalyst particles and the collision frequency. When the growth temperature was 600^oC, the as-grown CNTs in the array were with a mean diameter of 10.2 nm. If propylene was used as carbon source, the diameter can be modulated in similar trends. The diameter of CNT can be modulated by the parameter of the operation using the same substrate and catalyst precursor without other equipment or previous treatment. Those results provide the possibility for delicately controllable synthesis of CNT array via simple floating catalyst CVD.     

Growth of size-tunable periodic Ni silicide nanodot arrays on silicon substrates

The fabrications of size-tunable periodic arrays of nickel metal and silicide nanodots on (0 0 1)Si substrates using polystyrene (PS) nanosphere lithography (NSL) and heat treatments have been investigated. The growth of epitaxial NiSi₂ was found to be more favorable for the Ni metal nanodot arrays. The effect becomes more pronounced with a decrease in the size of the Ni nanodots. The sizes of the epitaxial NiSi₂ nanodots were tuned from 38 to 110 nm by varying the diameter of the PS spheres and heat treatment conditions. These epitaxial NiSi₂ nanodots formed on (0 0 1)Si were found to be heavily faceted and the faceted structures were more prone to form at higher temperatures. Based on TEM, HRTEM and SAED analysis, the faceted NiSi₂ nanodots were identified to be inverse pyramids in shape. Compared with the NiSi₂ nanodot arrays formed using single-layer PS sphere masks, the epitaxial NiSi₂ nanodot arrays formed from the double-layer PS sphere templates exhibit larger interparticle spacings and smaller particle sizes. Since the nanoparticle sizes, shapes and interparticle spacings can be adjusted by tuning the diameter of the PS spheres, stacking conditions, and heat treatment conditions, the PS NSL technique promises to be an effective patterning method for growth of other nanostructures.     

Synthesis and bioactivity of highly ordered TiO2 nanotube arrays

The highly ordered TiO₂ nanotube arrays were fabricated by potentiostatic anodization of Ti foils in fluorinated dimethyl sulfoxide (DMSO). TiO₂ nanotube arrays are formed using a 40 V anodization potential for 24 h, with a length of 12 μm, diameter of 170 nm and aspect ration of about 70. The as-prepared nanotubes are amorphous, but can be crystallized as the heat treatment temperature increases. Anatase phase appears at a temperature of about 300 °C, then transforms to rutile phase at about 600 °C. After heat treatment at 500 °C and soaking in SBF for 14d, a thick apatite layer of about 13 μm covers the whole surface of TiO₂ nanotube arrays, indicating their excellent in vitro bioactivity, which is mainly attributed to their high specific surface area and the anatase phase.     

Detailed profiling of CNTs arrays along the growth window in a floating catalyst reactor

We report a detailed longitudinal and depth profiles of multi-wall carbon nanotubes (CNTs) arrays synthesized using xylene and ferrocene in a floating catalyst reactor. Point to point analyses of the CNTs grown in a “growth window” with CNTs arrays longer than 0.5 mm were performed using optical microscopy, Raman spectroscopy, FESEM, high-resolution TGA/DTA, and TEM techniques. The heights of the CNTs arrays show a maximum at a mid point of the growth window, while a reverse trend of minimum is observed for iron-to-CNTs atomic ratios. The ratio of amorphous carbon to CNTs sharply increases along the growth window and from the bottom to top of CNTs arrays. The CNTs diameter also increases along the growth window, due to deposition of the amorphous carbon, which can be almost removed by temperature programmed oxidation up to around 500 °C. A base growth mechanism, the variations of catalyst content, residence time and temperature profile along the growth window, the adsorption and decomposition of polycyclic aromatic hydrocarbons to amorphous carbon, and a limited diffusion of hydrocarbon species through the arrays covered by excessive amorphous carbon may explain the results.     

Selective growth, characterization, and field emission performance of single-walled and few-walled carbon nanotubes by plasma enhanced chemical vapor deposition

Single-walled carbon nanotubes (SWCNTs) and few-walled carbon nanotubes (FWCNTs) have been selectively synthesized by plasma enhanced chemical vapor deposition at a relative low temperature (550 °C) by tuning the thickness of iron catalyst. The parametric study and the optimization of the nanotube growth were undertaken by varying inductive power, temperature, catalyst thickness, and plasma to substrate distance. When an iron film of 3-5 nm represented the catalyst thickness for growing FWCNT arrays, SWCNTs were synthesized by decreasing the catalyst thickness to 1 nm. The nanotubes were characterized by field emission scanning electron microscopy, transmission electron microscopy, and Raman spectroscopy. Electron field emission properties of the nanotubes indicate that the SWCNTs exhibit lower turn-on field compared to the FWCNTs, implying better field emission performance.     

Effect of calcination temperature on the morphology and surface properties of TiO2 nanotube arrays

Well-ordered TiO₂ nanotube arrays were prepared by electrochemical anodization of titanium in aqueous electrolyte solution of H₃PO₄ + NH₄F at a constant voltage of 20 V for 3 h, followed by calcined at various temperatures. X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS) and Photoluminescence (PL) were used to characterize the samples. The results showed that the as-prepared nanotube arrays before being calcined were amorphous and could transform to anatase phase at a heat treatment temperature higher than 400 °C. As the calcination temperatures increased, crystallization of anatase phase enhanced and rutile phase appeared at 600 °C. However, further increasing the calcination temperature would cause the collapse of nanotube arrays. PL intensity of the nanotube arrays annealed at 500 °C was the lowest, which was probably ascribed to better crystallization together with fewer surface defects of the nanotube arrays.     

Synthesis and properties of aligned ZnO microtube arrays

Two kinds of different aligned zinc oxide (ZnO) crystal microtube arrays were prepared on silicon (1 0 0) substrates by using of a simple thermal chemical reaction vapor transport deposition method. The synthesizing processes were done by using of heating the mixture of zinc oxide and graphite powders at 1150 °C in a quartz tube with one side opened to the air. The O₂ gas (99.9%) and air had been introduced as the assistant gases, respectively. Both the flow rates were 100 ml/min. And the temperature of the Si (1 0 0) substrate region was about 400 °C. There is no other metal catalyst on the Si wafers in the process. After growing for 30 min, one kind of synthesized sample is trumpet-shaped hexagonal microtube arrays assisted with O₂ gas and another produced sample is the uniform hexagonal microtubes only assisted with air. As the increasing of preparing time, their maximal lengths can range from several 10 μm to mm scale. The microstructure, room temperature photoluminescence properties and growth mechanism of both aligned microtube arrays were investigated and discussed.     

Optimization of a thermal-CVD system for carbon nanotube growth

We illustrate the optimization of the operation of a thermal chemical vapor deposition (CVD) system for the growth of carbon nanotubes (CNT). We have studied the deposition parameters using the Taguchi matrix robust design approach. The CVD system, which employs solid precursors (camphor and ferrocene) carried by nitrogen gas flow through a hot deposition zone, where the deposition of carbon nanostructures takes place, involves a large number of tunable parameters that have to be optimized.With the aim of getting the best configuration for the development of massive and well-oriented CNT carpets, the Taguchi method allowed us to improve our system leading to the growth of extremely long CNTs (few millimeters) at a high deposition rate (500 nm/s) and yield (30% in weight of the carbon precursors feedstock), which were characterized by electron microscopy.We found that the growth temperature had the most important influence on the CNT diameter, whereas the substrate tilt wit respect to gas flow did not influence their growth (i.e. CNTs grow on every side of the silicon wafer substrates, always normal to the substrate surface). The carrier gas flow and catalyst concentration both showed a secondary impact on CNT growth, though they showed a consistent correlation to the growth temperature.     

Growth of Ag nanoclusters on a 1D template

Bi nanolines, which are 1.5 nm wide and can be over 500 nm long, have been used as a 1D template for the formation of arrays of small clusters of silver. Distinct nucleation and growth phases are observed. At room temperature, silver atoms preferentially adsorb onto the Bi nanoline templates to form arrays of spheroidal nanoclusters 0.55 nm in height, up to a saturation density of 6.7 clusters per 100 nm of nanoline. Further deposition of Ag results in the growth of the clusters on the nanolines up to 1.4 nm, accompanied by the formation of 0.55 nm clusters on the background. At 400 K, however, deposition of Ag results in the formation of clusters up to 4 nm in height, with the majority formed on the nanoline template.     

Effects of thermal annealing temperature and duration on hydrothermally grown ZnO nanorod arrays

In this study, the effects of thermal annealing temperature and duration on ZnO nanorod arrays fabricated by hydrothermal method were investigated. The annealed ZnO/Si(1 1 1) substrate was used for ZnO nanorod array growth. The effects of annealing treatment on the structural and optical properties were investigated by scanning electron microscopy, X-ray diffraction, and room-temperature photoluminescence measurements. With the annealing temperature of 750 °C and the annealing duration of 10 min, both the structural and optical properties of the ZnO nanorod arrays improved significantly, as indicated in the X-ray diffraction and photoluminescence measurement.     

Effect of micro and nanoparticle inorganic fillers on the field emission characteristics of photosensitive carbon nanotube pastes

We successfully fabricated field emitter arrays of carbon nanotube (CNT) dots of 10 μm diameter with excellent field emission properties by using photosensitive CNT paste. The CNT paste was investigated in terms of morphologies, current-voltage properties, and luminous uniformities by varying the mixing ratios of micro and nanoparticle inorganic fillers and the amount of CNTs added into the paste. The 3:1 mixing of micro and nanoparticle fillers and the addition of 5% CNTs in the paste brought about the best field emission characteristics of dot-patterned CNT field emitter arrays.     

Effects of different carbon precursors on synthesis of multiwall carbon nanotubes: Purification and Functionalization

Cyclohexanol and xylene were used as carbon precursors, for synthesis of multiwall carbon nanotubes (MWCNTs) arrays in a CVD system at temperature of 750 °C, using nitrogen as carrier gas and ferrocene as catalyst. Different characterization methods were employed to compare the MWCNTs structure synthesized by these two precursors. All scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermal gravimetric analysis (TGA) and Raman spectroscopy results illustrated that using cyclohexanol could significantly reduce formation of amorphous carbon and catalyst particles in the as-grown CNTs. The less amorphous carbon can be attributed to in situ oxidation in presence of oxygen atom of cyclohexanol. Characterizations showed that MWCNTs with high purity could be obtained using cyclohexanol as carbon precursor. The as-grown MWCNTs were purified by oxidation and acid treatment. Characterization of the purified MWCNTs using HNO₃/H₂SO₄ (1/3 or 1/1), 8 M HCl or 8 M HNO₃ was carried out. The results showed that 8 M HNO₃ could be considered as the best chemical to obtain more pure MWCNTs, less amorphous and metal particles and less damaged MWCNTs. The Raman spectroscopy results demonstrated that HNO₃/H₂SO₄ (1/3) treatment could more disorder the MWCNTs structure and this was attributed to the bigger destroying effect of this acid treatment. Furthermore, the TEM analysis of MWCNTs before and after acid treatment revealed that acid treatment could remove encapsulated catalyst particles. The FTIR analysis illustrated that purification of the MWCNTs with nitric acid could connect the functional groups onto the outer surface of MWCNTs and this resulted in more dispersion of the MWCNTs in water.     

Monolayer deposition of L10 FePt nanoparticles via electrospray route

The deposition monolayers of L1₀ FePt nanoparticles via an electrospraying method and the magnetic properties of the deposited film were studied. FePt nanoparticles in a size of around 2.5 nm in diameter, prepared by a liquid process, were used as a precursor. The size of the deposited particles can be controlled up to 35 nm by controlling the sprayed droplet size that is formed by adjusting the precursor concentration and the precursor flow rate. The droplets were heated in a tubular furnace at a temperature of up to 900 °C to remove all organic compounds and to transform the FePt particles from disordered face centered cubic to an ordered FCT phase. Finally, the particles were deposited in the form of a monolayer film on a silicon substrate by electrostatic force and characterized by scanning electron microscopy. The monolayer of particles was obtained by the high charge on particles obtained during the electrospraying process. The magnetic properties of the monolayer were investigated by magneto-optic Kerr effect measurements. Coercivity up to 650 Oe for a film consisting of 35 nm L1₀ FePt nanoparticles was observed after heat treatment at a temperature of 800 °C.     

A template-free sol-gel technique for controlled growth of ZnO nanorod arrays

The growth of ZnO nanorod arrays via a template-free sol-gel process was investigated. The nanorod is single-crystalline wurtzite structure with [0 0 0 1] growth direction determined by the transmission electron microscope. The aligned ZnO arrays were obtained directly on the glass substrates by adjusting the temperatures and the withdrawal speeds, without seed-layer or template assistant. A thicker oriented ZnO nanorod arrays was obtained at proper experimental conditions by adding dip-coating layers. Room temperature photoluminescence spectrum exhibits an intensive UV emission with a weak broad green emission as well as a blue double-peak emission located at 451 and 468 nm, respectively. Further investigation results show that the difference in the alignment of nanorods ascribes to the different orientations of the nanoparticles-packed film formed prior to nanorods on the substrate. Well ordered ZnO nanorods are formed from this film with good c-axis orientation. Our study is expected to pave a way for direct growth of oriented nanorods by low-cost solution approaches.     

Effects of Ni catalyst–substrate interaction on carbon nanotubes growth by CVD

An investigation of the effects of substrate type and various treatments on carbon nanotubes (CNT) growth, using an evaporated Ni thin film as a catalyst, is presented. Barrier layers of SiO₂, Si₃N₄, and TiN on Si were used as substrates. The catalyst-insulating substrate systems have been processed in several gaseous atmospheres (Ar, NH₃ and H₂) and in the temperature range 700–900 °C, in order to obtain the most appropriate morphology, size and density of catalyst particles as seeds for the subsequent CNT growth. On this kind of substrates, the smallest nanoparticles were obtained on SiO₂ layers, in H₂ or NH₃ atmosphere even at 700 °C. However, the best vertically aligned and well-graphitized CNT resulted from the NH₃ annealing process, followed by the CNT deposition at 900 °C in C₂H₂ and H₂.On TiN conducting substrates, the best vertically aligned CNT were deposited using a shorter annealing step and a deposition process at reduced pressure. The samples were characterized by means of scanning electron microscopy (SEM) and Raman spectroscopy analysis.     

Influence of chemistry and hot rolling conditions on high permeability non-grain oriented silicon steel

This paper discusses the influence of chemical composition on the final electromagnetic properties in higher permeability material. Furthermore, the effect of the hot rolling practice and the end of austenite transformation temperature range on the hot band microstructure is described. The magnetic polarization J₅₀₀₀ better than 1.7 T, using hot rolling conditions 40 mm transfer bar thickness, finish mill entry temperature 1000 °C, and finishing temperature 800–840 °C and after decarburization heat treatment and grain growth treatment, was obtained.     

Preparation of vertically aligned carbon nanotube arrays grown onto carbon fiber fabric and evaluating its wettability on effect of composite

Vertically aligned carbon nanotube (CNT) arrays have been grown onto the carbon fiber fabric using a catalytic chemical vapor deposition (CCVD) method. The as-synthesized CNT arrays are about 20 μm in height, and the nanotube has a mean inner and outer diameter of 2.6 nm, 5.5 nm, respectively. The CNT-grafted carbon fabric shows a hydrophobic property with a contact angle over 145°, and the single CNT-grafted carbon fiber shows a sharp increase of dynamic contact angle in de-ionized water from original 71.70° to about 103°, but a little increase does in diiodomethane or E-51 epoxy resin. However, the total surface energy of carbon nanotube-grafted carbon fiber is almost as same as that of as-received carbon fiber. After CNTs growth, single fiber tensile tests indicated a slight tensile strength degradation within 10% for all different lengths of fibers, while the fiber modulus has not been significantly damaged. Compared with the as-received carbon fibers, a nearly 110% increase of interfacial shear strength (IFSS) from 65 to 135 MPa has been identified by single fiber pull-out tests for the micro-droplet composite, which is reinforced by as-received carbon fiber or CNT-grafted carbon fiber.